3 FINAL G10 Feasibility Report

KKEK 4281 DESIGN PROJECT ACRYLONITRILE PRODUCTION FROM SOUR CRUDE OIL
FEASIBILITY REPORT (RAPID) GROUP 10
CHAPTER 1: INTRODUCTION
When talking about the petrochemical industry, most of the people will first imagine about the production of the car fuel, plastic products or even the cooking gas. However, the industry is indeed more than that. Various types of products can be derived from the raw fossil fuels, depending on the projects that the producers are working on. RAPID with its full name Refinery and Petrochemical Integrated Development is the focus on this Design Feasibility Study report. In this report, RAPID major production components are the proposed refinery with refining capacity of 150,000 barrels-per-day sour crude oil and acrylonitrile production plant with an annual production of approximately 120,000 tons per annum.
1.1 SOUR CRUDE OIL Basrah sour crude oil from Middle East (Iraq) is being chosen as the main raw material for the process production. The term sour is used due to its high content of impurity sulphur, and thus it needs to be refined into sweet crude oil before it can proceeds to the next process. Based on statistic, Iraqs oil exports rise to an average of 2.565 million barrels per day in August, 2012 from 2.516 million barrels per day in July, 2012. This is recorded to be the highest level in three decades (according to Reuters).[1] Figure 1.1 shows the present and the forecast crude oil production of some oil producer country such as Iraq, Brazil, Canada, Nigeria and Russia.
Figure 1.1: The current and expected statistics for the capacity of crude oil producers.
[2]
As can be seen, the expected producing rate of crude oil for Iraq is positive in the next 10 years. This is due to the Iraqs government proactive plans, such as securing license for several
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existing oil field. This intends on expanding the production capacity of the crude oil on its fullest potential. [2] Therefore, sour crude oil is imported from Basrah, Iraq (Middle East) to be the feedstock of the refinery plant in this RAPID design project.
1.2 ACRYLONITRILE Acrylonitrile is chosen as the final product for this RAPID design project. Basically, the primary uses for acrylonitrile are the chemical intermediate in acrylic fibres, ABS (acrylonitrilebutadiene-styrene), SAN (styrene-acrylonitrile), NBR (nitrile-butadiene-rubber), acrylamide (manufacture of various polymers) and adipronitrile (used to make Nylon 6,6). This is due to its extensive commercial and industrial applications as tough, durable synthetic rubbers and engineering plastics.[3, 4] The percentage of the applications of acrylonitrile is presented in a pie chart as shown in figure 1.2.
Applications of Acrylonitrile
Other uses 18%
Acrylamide, A dipronitrile 15%
Fibres 52%
ABS and SANS 15%

Figure 1.2: The percentage uses of acrylonitrile. [4]
In addition, acrylonitrile is also used in manufacturing of polyacrylonitrile (PAN) for acrylic fibre, this is used in apparel, household furnishings, industrial markets and applications. Besides, acrylonitrile is the chemical intermediates to synthesis various antioxidants, pharmaceuticals, dyes and surface-active.
In the year of 2007, global demand on acrylonitrile reaches the highest peak but it was decreased by about 13% in 2008, which was resulted by the global economic downturn. However,
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in the beginning of the year 2009, the global demand recovered at an average annual rate of 5%. The bulk growth of acrylonitrile demand is taking place in Asia, and it is driven by the constant development of the electrical appliances and also the automotive industries. The bar chart below depicts the global acrylonitrile consumption for the year 2011 for various countries. [5]
Percentage of World Acrylonitrile Consumption in 2011

40 35
30
25 20 15 10 5 0 China Other Asia Western Europe North America Japan Others
Figure 1.3: The percentage uses of Acrylonitrile consumption according to region in 2011. [5]
As can be seen, the highest demand comes from China and other parts of Asia. It is positive news for the plant project, as the targeted market for the plant product is Malaysia, China, India and also Indonesia.
1.3 REFERENCES [1] Lee, J., Iraqi Oil Exports Hit New Highs. (2012). Retrieved 8 October 2012, from http://www.iraq-businessnews.com/tag/somo/ [2] Purvin, G.H., Crude Demand to increase, Feed Quality Changes in store. (2010). Retrieved 8 October 2012, from http://www.ogj.com/articles/print/volume-108/issue46/processing/crude-demand-to-increase-feed-quality.html [3] Tech., I., Acryonitrile properties. (2012). Retrieved 8 October 2012, from http://www.ineostechnologies.com/83-process.htm [4] Europe, A.o.P.P.i., Acrylonitrile usage and properties. (2012). Retrieved 8 October 2012, from http://www.petrochemistry.net/acrylonitrile.html [5] Chemical, IHS., Acrylonitrile. (2012). Retrieved 8 October 2012, from http://www.ihs.com/products/chemical/planning/ceh/acrylonitrile.aspx
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CHAPTER 2: FEEDSTOCK
2.1 SELECTION OF CRUDE OIL PRODUCER
By referring to the world oil reserved graph as shown in figure 2.1, the largest oilproducing exporter is in the Middle East as every country in the middle east are an oil-rich and the term Middle East and oil-rich are often taken together as synonym. Iraq, one of the countries in the Middle East is selected to be the best option for the oil supplier. Table 2.1 is the break, by table ranking Middle Easts oil-rich countries according to known oil reserves.[1]
World Oil Reserves by Region

Africa 9% Asia & Oceana 3%
Middle East 56%
North America 16%
Eurasia 7%
Central & South Europe America 8% 1%
Figure 2.1: World Oil Reserves by Region in 2007[1]. Table 2.1: The Middle East's Oil Producer. [1] Rank Country Reserves (billions of barrels) 1 2 3 4 5 6 Saudi Arabia Iran Iraq Kuwait United Arab Emirates Libya 262.3 136.3 115 101 97.8 41.5
2.1.1
Supporting Facts and Reasoning The source of crude oil is obtained directly from Basra Oil, Iraq which is located in the
Middle East. Basra (34.4 API and 2.10% sulphur)[2] is high-grade oils, the light and average sulphur content most similar to the Arab Light grade from Saudi Arabia. Even though Iraq is in 3rd rank, it has highest reserve life (proven reserves/annual production) of all oil producers. It has vast and relatively undeveloped oil resources. Iraq also has a large south-western desert territory that has not yet been fully explored and is estimated to contain up to 100 billion barrels of additional oil reserves[3]. Saudi Arabia which is in the 1st rank is not chosen as the oil supplier due to some speculation that Saudi consumption of oil would outstrip production and they could importing oil instead of exporting it [4]. Hence, to avoid such problem in the future for oil supplier, Basra Oil, Iraq is chosen over Saudi Arabia. Table 2.2: The distillation yields (% wt) of Basra Oil, Iraq. [5] Distilation Yields (% wt) C1 to C4 Naphtha (C5 to 149 C) Kerosene (149 C to 232 C) Gas oil (232 C to 342 C) Atmospheric Residue (342 C +) Basra Oil 1.6 14.4 12.5 17.1 54.5
According to BP Statistical Review of World Energy, June 2011, Iraq is the world 3 rd largest oil reserve capacity country, with 115 billion barrels of oil reserve. On December 11 2009, Iraq Oil Minister Hussain al-Shahristani confirm the trade agreement between Iraq and Malaysias state-run oil company, Petronas together with European oil giant, Shell, where both companies has won the rights to develop Iraqs giant Majnoon oil field, an almost 13 billion barrel behemoth. The trade agreement last for 20 years and approved by Iraqs cabinet. Hence, the feedstock availability is stable and reliable for the future coming years.
2.2
MARKET SURVEY ON FEEDSTOCK FOR ACRYLONITRILE This section will determine which type of feedstock is more feasible option for this new
acrylonitrile plant. The major hydrocarbon sources used in producing propylene are Methane, Ethane, Butanes which is obtained primarily from natural gas processing plants and Naphtha and Gas Oil which are obtained from petroleum refineries.
1992
Gas Oil Butane 7% 4% Propane 11% Naphtha 50%
Ethane 26% Others 2%
Figure 2.2: Feedstock for Olefins Production in Year 1992.[1]
Gas Oil Butane 7% 5% Propane 12%
2012
Naphtha 52%
Ethane 23% Others 1%
Figure 2.3: Feedstock for Olefins Production in Year 2012[2] Relatively small amount of propylene is produced when natural gas is used as the feedstock while a comparatively significant amount of propylene is produced when crude oil is used[6]. Naphtha which is produced from crude oil through refinery process shows highest percentage among the five feedstocks as shown in Figure 2.2 and Figure 2.3. It is decided to choose Basra Oil from Iraq as the crude oil supplier and the facts and reasoning as stated before.
2.2.1
Naphtha Naphtha is used as the feedstock for fluid catalytic cracking process to produce the co-
products which are propylene, ethylene and butadiene. In general, there are two types of naphtha which are light naphtha and heavy naphtha. Light naphtha consists of molecules with 5 to 6 carbon atoms whereas heavy naphtha consists of molecules with 6 to 12 carbons.
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2.2.2 Comparison of Light and Heavy Naphtha Table 2.3 below summarized the comparison between Light Naphtha and Heavy Naphtha. Table 2.3: Comparison between Light and Heavy Naphtha as feedstock. Factors Paraffin content Light Naphtha High
[2]
Heavy Naphtha Less and contain more aromatic compound. 85-190[2]
Approximate Range,oC Major product
Boiling
25-90
Olefins products Require less than heavy naphtha.
Aromatic products Require high operating
Cracking temperature
temperature of cracking furnace.
From the comparison, when the major products desired are olefins, light naphtha will be the favoured feedstock whereas heavy naphtha are used as feed in plants that desired to produce aromatic products. Heavy naphtha requires that the cracking furnaces be operated at relative higher temperatures compared to light naphtha feed in order to obtain the same yield percentage. Light Naphtha was chosen over heavy naphtha as it yields more olefins and required less stringent furnace operating conditions and has a lower rate of coking.
2.3 CONCLUSION In a nutshell, Light Naphtha is the best option rather than heavy naphtha as our feedstock due to reason as below: a) Higher yield of olefins. b) Lower coking rate. c) Less stringent furnace operating conditions. The feedstock Basra Oil will be shipped from Iraq, Middle East to the proposed plant location, Pengerang Port, Johor.
2.4 REFERENCES [1] Wang, S. and E. Ariyanto, Competitive adsorption of malachite green and Pb ions on natural zeolite. Journal of Colloid and Interface Science, 2007. 314(1): p. 25-31. [2] Brown, J. Quality Or Quantity. (2011). Retrieved 5 December, 2012, from http://www.oilslick.com/commentary/?id=2332&type=1. [3] Avery, C., Iraqi Oil Industry. (2010). [4] Aluwaisheg, A.A., Will Saudi Arabia become an oil importer by 2030, in Arab News. (2012). [5] BP, L.I.O. Basra Light. (2012). Retrieved 5 December, 2012, from http://www.bp.com/extendedsectiongenericarticle.do?categoryId=9035920&contentId=70665 56. [6] Gazette, S. Demand driven by packaging, automotive sectors Retrieved 8 December 2012, from http://www.gulfinthemedia.com/index.php?m=economics&id=536655&lim=180&lang=en&t blpost=2010_10&PHPSESSID=8.
CHAPTER 3: PRODUCTS AND CO-PRODUCT

3.1 MARKET SURVEY This market survey will only focus on the Asia region, which including 4 major markets such as Malaysia, China, India and last but not least Indonesia. Figure 3.1 shows the potential demand of Asia is huge especially from year 2013 to year 2018.
Figure 3.1a: The Production and Demand of Acrylonitrile in Various Regions in year 2013
[9]
Figure 3.1b: The Production and Demand of Acrylonitrile in Various Regions in year 2018
[9]
. From Figure 3.2a and Figure 3.2b, there is huge potential in Asias acrylonitrile demand
market, where China and India are determined to be stable net importers of acrylonitrile. The capacity demanded is always higher than the production rate. This shows that China and India, which has 35 % world population (2.3 billion out of 7 billion) are indeed a huge goldmine for acrylonitrile market.
Figure 3.1 c: The Acrylonitrile Capacity Utilisation in China [9].
Figure 3.1 d: The Acrylonitrile Capacity Utilisation in India [9]. Table 3.1 shows the planned addition of acrylonitrile capacity in the Asia for the future five years.
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Table 3.1: Planned Additions of Acrylonitrile Capacity [9].
From Table 3.1, it can be deduced the regional total capacity of acrylonitrile is only 2603 000 tons, which is far more less than the minimum capacity needed, 3000 000 tons shown is Figure 3.1a. Moreover, BP CHEMICALS estimates that global acrylonitrile demand will grow by 3% per year, helped largely by China. This would require an extra 150 000 tonne of supply annually
[2]
.Furthermore, according to Asahi Kasei Chemicals, acrylonitrile demand in Asia
region is forecast to grow at 5% constantly [1] .Hence, it can be concluded that selling acrylonitrile to Asia Region was economically feasible in this modern times. Such a conclusion was supported by Mr Yee Nai Tuck, Senior Deputy Director of Malaysian Investment Development Authority (MIDA) on 27th October 2012 during his seminar talk at Chemical Engineering Department of University Malaya. (It is left to the reader to decide the reliability of his opinion)
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3.2 CO-PRODUCT HYDROGEN CYANIDE Direct production accounts for about 70% of the total capacity and the balance is derived as co-product material from acrylonitrile production. The following pie chart shows world consumption of hydrogen cyanide:
Figure 3.2 World Consumption of Hydrogen Cyanide. [2] Between 2005 and 2009, total consumption of hydrogen cyanide in the United States, Western Europe and Japan increased by about 2% per year. Global consumption is expected to increase at an average rate of around 12% per year from 2009 through 2019, assisted by increased demand for nutritional additives and higher demand market from Asia countries, especially China and India, although the increased consumption in Western Europe was offset by reductions in Japan (due to nuclear meltdown incidents in Fukushima, it affects the world petrochemical market) and stagnation in the United States resulting from reduced demand for adiponitrile[2]. The major end uses for hydrogen cyanide include adiponitrile and sodium cyanide. Due to its toxicity, hydrogen cyanide is usually consumed at its site of production. In March 2012, PETRONAS and BASF have entered into a Heads of Agreement (HOA) for the RAPID.
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Under the terms of the HOA, the partners have agreed to form a joint venture (BASF 60%; PETRONAS 40%) to develop, construct and operate production facilities for several petrochemical products, and one of product goes to adiponitrile. Hence, the by-product hydrogen cyanide will be sold to BASF plant for further processing into adipontrile. 3.3 CO-PRODUCT ACETONITRILE Acetonitrile is a co-product in the manufacture of acrylonitrile by ammoxidation of propylene at a rate of about 23% of acrylonitrile production. The following pie chart shows world consumption of acetonitrile:
Figure 3.3 World Consumption of Acetonitrile. [2] Consumption of acetonitrile in the pharmaceutical and analytical industries has experienced solid growth. The pharmaceutical industry is the largest end use for acetonitrile. It is estimated that approximately half of China's consumption of acetonitrile is for the production of vitamin B1, half of which is then exported worldwide. The use of acetonitrile in pharmaceutical products for diseases has grown rapidly in recent years, boosted by improved living standards in industrialized countries. Consumption of acetonitrile for pharmaceuticals will continue to grow during the next five years, which is from year 2011 to 2016.
World consumption is forecast to continue to grow at a rate of about 5% per year over the next five years. The highest growth rate (about 89% per year) is expected for China and India, because of the increasing production of engineered drugs, generic pharmaceuticals and pesticides in these countries. In Europe (including Switzerland) and in the United States, the annual growth
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rate for 20102015 is estimated at 2%. Hence, the separation of acetonitrile from the main final product will be an economic feasible and profitable plan, besides that focusing only on the main product, acrylonitrile.
3.4 DESCRIPTION OF SOURCE AND DEMAND COUNTRIES. Over the world there are vast producers of acrylonitrile specifically from Europe, Asia, America and Middle East. The proposed plant of this acrylonitrile plant will focus more on the demand countries like China, Indian, Malaysia and Indonesia and some of the Asias producers are Japan, South Korea, Taiwan and Thailand. 3.4.1 China [3] China is the largest acrylonitrile producer in Asia region with higher number of producers such Anqing Petrochemical, Daqing Refining & Chemical ,Fushun Petrochemical Co, Jilin Petrochemicals Ltd (JLPL), Lanzhou Petrochemical Corp, Maoming Petrochemical Corp (MPCC) (Shenzhen SE), Ningbo Shunze Rubber Co, Qilu Petrochemical Co Ltd and Sinopec Corp. Acrylonitrile prices have been climbing up and this force to China increase the production over the years and focusing more on the concerned issues regarding the development of acrylonitrile and its by product. They also promote and encourage producers, traders and downstream customers to exchange info and ideas regarding the strong development of acrylonitrile. In the 9th China International Acrylonitrile Forum on 8th March 2012, China has revealed their new import trade of raw material from South Korea, Taiwan and Japan will hike up in order to fulfil with their demand of acrylonitrile in the country and creating over opportunity to expand globally. China is subjected to remain one of the market importers with 20% market dependency for the coming 5 years. 3.4.2 India [4] India has starting steps for acrylonitrile but from Acrylonitrile Industry Outlook in India to 2016, they had capacity forecast to be increase and their market trends will be the new development for acrylonitrile. Reliance Industries Ltd is the major acrylonitrile producer in India and their market size was comparably small, with 50,000 tons (refer Table 3.1) acrylonitrile per annum. However, India require an import demand of 1650,000 tons (refer figure 3.1b) acrylonitrile per annum in 2013 even with its current expansion plan, moreover with statistic support that their import demand will keep hiking up with 4% per annum. India has begun with
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their new benchmark where they proposed to have new market entry and market expansion within 2016. 3.4.3 Japan [5] Japans Acrylonitrile industry has a consistent plant capacity growth and major of its product were exported. Their trading amount of acrylonitrile to other part of Asia country leads the growth of acrylonitrile in Japan. Current acrylonitrile producer in Japan are Asahi Kasei Corp, Dia-Nitrix Co Ltd, Showa Denko KK (Shoden) and Sumitomo Chemical Co Ltd. They had a dynamic strength from year 2000 and predicted that the strength in acrylonitrile production will goes on till 2016 in Asia region. However, due to nuclear meltdown incidents in Fukushima on year 2011, it affects the world petrochemical market and reductions in production of acrylonitrile in Japan. Japan has in fact intends to reduce its acrylonitrile production by 5-7 % over the next 5 years due to saturation of demand in Japan[8] .This will no doubt that shortage of acrylonitrile will happen in Asia due to strong demand dominated by China and India. With the introduction of our plant, we can get a piece of cake in both countries. 3.4.4 Malaysia [6] Malaysia has quite availability of hydrocarbon feedstock from oil and gas and the acrylonitrile production in Malaysia is in the form of acrylonitrile-butadiene (ABS). There are futures developments in the country where a petrochemical zone will be build and the acrylonitrile production will be enhance. Malaysia has the investment contribution and technology development where the acrylonitrile production can be enhance according to Industrial Master Plan (IMP) 2006-2020. The new petrochemical zone in Malaysia is targeting to develop new product and expand the manufacturing with the growth of the market size globally.
3.5 PRODUCT PRICING Based on the Figure 3.5 below, the acrylonitrile price globally has its own trend and mostly on every first quarter of each year it shows a good hike up and steady increase, and the following of the year there are drop in the price trend and hike up again. The price trend was most affected by weather factor and transportation. First quarter of the year seem the best weather conditions and less transportation problem faced by the producer to deliver the product, so it creates a higher prices trend with higher trade demand. In some circumstances, when the
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delivering of product challenge by the weather factor and transportation, the price goes down as the demand of trade go slow on this period due to the risk of undeliverable material.
The price of acrylonitrile in year 2011 is higher than year 2012, this is due to the demand remain sluggish in Europe and United States.
Figure 3.4: Global Acrylonitrile Price Trend. [7]
3.6 CONCLUSION From the reviewing of the market survey up to date, its stated clearly that production of acrylonitrile in the Malaysia can shoot up the market over the Asian countries as the demand as continual increment over year. The proposed acrylonitrile plant has production capacity of 120,000 tons per year which are wide enough to cover the demand supply. Based on the brighter demand of acrylonitrile in Asia and its global market price as tend be an increment of 4% annually gives the best financial outcome thus as schedules the acrylonitrile plant will be commissioned within 2015 to 2016 in Malaysia.
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3.7 REFERENCES [1] BP considers SEA acrylonitrile plant. Retrieved 31 October 2012, from http://www.icis.com/Articles/2004/06/18/590273/bp-considers-sea-acrylonitrile-plant.html [2] Chemical Insight and Forecasting: IHS Chemical. Retrieved 31 October 2012, from http://www.ihs.com/products/chemical/planning/ceh/hydrogen-cyanide.aspx [3] 7th China International Acrylonitrile & Acrylic Fiber Forum. Retrieved 31 October 2012, from http://www.fibre2fashion.com/news/fibre news/news details. aspx? news_id=81764. [4] Acrylonitrile Industry Outlook in India to 2016 Market Size, Company Share, Price Trends, Capacity Forecasts of All Active and Planned Plants. Retrieved 31 October 2012, from http://www.researchandmarkets.com/reports/2228353/acrylonitrile_industry _outlook_in_india_to_2016. [5] Acrylonitrile Industry Outlook in Japan to 2016 - Market Size, Company Share, Price Trends, Capacity Forecasts of All Active and Planned Plants. Retrieved 31 October 2012, from http://www.marketresearch.com/GlobalData-v3648/Acrylonitrile-Outlook-Japan-SizeCompany-7126611. [6] The Malaysian Petrochemical Industry. Retrieved 31 October 2012, from http://www.malaysia.ahk.de/fileadmin/ahk_malaysia/Market_reports/The_Malaysian_Petroc hemical_Industry.pdf [7] Global Indepth Acrylonitrile Analysis. Retrieved 31 October 2012, from http://www.yarnsandfibers.com. [8] Newswire, P. Acrylonitrile Global Market to 2020 - Household appliances and electronics sector to drive Acrylonitrile Butadiene Styrene (ABS) growth, polymeric applications propel Polyacrylonitrile demand from Asia-Pacific. (2012). Retrieved 8 December 2012, from http://finance.yahoo.com/news/acrylonitrile-global-market-2020-household-123900271.html [9] PCI , A.L., <PCI Acrylonitrile Supply Demand Report 2009 B.pdf>. 2009
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CHAPTER 4 TECHNOLOGY PROCESS ROUTES

There are plenty of process routes available for the cracking process to produce olefin such as propylene; also to produce acrylonitrile. In this chapter, discussion on the steam cracking and fluid catalytic cracking is performed in section 4.1, whereas section 4.2 is the comparison on the propylene ammoxidation and propane ammoxidation.
4.1 PROPYLENE PRODUCTION For the production of propylene from the light naphtha feedstock after the hydro-treating plant, the common cracking processes are steam cracking and fluid catalytic cracking. Cracking processes carry out chemical reactions that fracture or crack the large, highboiling hydrocarbon molecules into smaller and lighter molecules, which are suitable for further processing. There are several cracking unit such as steam cracking, fluid catalytic cracking and hydrocracking.
[1]
However, two primary interest cracking units will be discussed further in this
report which is steam cracking unit and fluid catalytic cracking unit.
4.1.1 Steam Cracking Steam cracking is mainly a free radical reaction which generates C2 components. There is no catalyst needed in the steam cracking process. Without the presence of the catalyst, high reaction temperature is thus required, which is at 750-850C [2]. Besides, propylene content of C3 stream is about 50%. [3]
4.1.2 Fluid Catalytic Cracking (FCC) The catalytic cracking is where -scission occurs under the existence of catalyst cracking through carbocation intermediate. radical.
[4] [4]
Carbocation is longer lived and more selective than free
High yields of C3, C4 olefins can be obtained such that propylene content of C3 stream
is about 70%. [3] Catalytic cracking breaks complex hydrocarbons into simpler molecules in order to increase the quality and quantity of lighter, more desirable products and decrease the amount of residuals. Use of a catalyst in the cracking reaction increases the yield of improvedquality products under much less severe operating conditions than in thermal cracking, for example reaction temperature in the range of 454.44-510C
[5]
The catalysts used are typically
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solid materials (zeolite, aluminium hydrosilicate, treated be ntonite clay, fullers earth, bauxite, and silica-aluminium) that come in the form of powders or beads.[5] On the other hands, the good sides, bad sides and the solutions of the drawback are discussed in the Table 2 below.
Table 4.1: Comparison of the good sides and bad sides of the steam cracking and catalytic cracking processes. STEAM CRACKING CATALYTIC CRACKING ADVANTAGES High yield with high temperature in Produces high-octane gasoline and fuel [2] the cracking furnaces. oils. [4] The process is stable, flexible and Reduce formation of olefinic under control both for liquid and gas hydrocarbons, which form gum deposits in [2] feeds. gasoline. [1] Proper control valve performance in furnace improves the accuracy of throughput control to the plant performance. [2] Produce hydrocarbons with high antiknock properties. [1]
Better selectivity. [4] Effect of the catalyst, which promotes isomerisation and dehydrocyclization reactions. [4] Reduce formation of methane and C2 hydrocarbon gases in favour of C3 and C4 hydrocarbons used in LPG. [1] DISADVANTAGES Furnace is operated at very high Nitrogen compounds are readily adsorbed temperature and pressure compared to on the catalyst acid sites and cause FCC. deactivation.[4] Lower yield of propylene. Polycyclic aromatics and asphaltenes contribute strongly to coke formation. It requires regeneration of the catalyst. [4] Coke formation on catalyst is substantially reduces its activity and produces gasolines of lower quality. [4] SOLUTIONS Feedstocks are often pretreated to decrease the metallic and asphaltene contents. [4] Hydrotreatment, solvent extraction and propane deasphalting are important
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treatment processes. [4] Modification of the composition and microporous structure of catalyst or adding metals like Sb, Bi or Sn or Sb-Sn combination. [4] 4.1.3 Decision Making Accordingly, with regards to increasing propylene production, it is more advantages to have a catalytic cracking-type reaction than a steam cracking type reaction.
[6]
Based on the table
2, FCC is advantageous than steam cracking. The main reason is that FCC gives high yield of propylene which is the desired feedstock for acrylonitrile production. By using appropriate catalyst, lower operating temperature and pressure are required compared with steam cracking. Although coking deposition on the catalyst may decrease the catalytic activity, but there is regenerator installed to regenerate the catalyst and remove the coke.
4.1.4 References [1] An introduction to petroleum refining and the production of ultra low sulphur gasoline and diesel fuel. The international council on clean transportation. Retrieved 9 October 2012, from www. Mathproinc.com [2]Steam cracking furnaces. Retrieved 28 September 2012, from http://valveproducts.metso.com/neles/ApplicationReports/2722_Petrochemical/2722_01_08e n.pdf [3]PERP ProgramPropylene. Retrieved 9 October 2012, from http://www.chemsystems.com/about/cs/news/items/PERP%200607_3_Propylene.cfm [4] S. Matar & L.F. Hatch. (1994). Provides quick and easy access to hundreds of reactions, processes and products. Chemistry of petrochemical processes. Second eds. United States of America: Gulf Publishing Company. [5] Cracking. The Encyclopedia of Earth. Retrieved 28 September 2012, from http://www.eoearth.org/article/Cracking [6] Kitaminato-machi, Wakamatsu-ku & Kitakyushu-shi. More Propylene in FCC Units. Catalyst Research Center. JGC Catalysts and Chemicals Ltd.
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4.2 ACRYLONITRILE PRODUCTION 4.2.1 Propylene Ammoxidation Propylene ammoxidation is a process in which mixtures of propylene, ammonia, and oxygen are converted in the presence of a catalyst, with acrylonitrile as its primary product. It is also known as ammonoxidation oroxyamination. [1] The catalyst selected for propylene ammoxidation should be multifunctional and possesses redox properties. Among commonly employed catalyst contains molybdenum or antimonium oxides mixed with transition metals, such as Ferum, Nickel, Copper and Vanadium, and activated by alkali and rare earth elements.[2] Table 4.2 below summarized the advantages and disadvantages of propylene ammoxidation.
Table 4.2 : Advantages and disadvantages of propylene ammoxidation. Advantages 1. The reaction rate is higher.[2] 2. Less cost required in operation because there is no need for excess ammonia and H2SO4 that is required for ammonia neutralization. 3. Lower capital cost for wastewater disposal. Disadvantages 1. Raw material price much expensive than propane. (50% of differences).[3] 2. Productivity levels are comparable to those obtained with propane.[3] 3.The co-products formation, such as acetonitrile (ACN) and hydrogen cyanide (HCN) are minimized, which would have a high value in the chemical market.[3] 4. Risk of propylene shortage due to its increasing consumption and worldwide demand of nitriles and other derived products.[3]
4. Adsorption rate of propylene is 10 times bigger than propane. 5. The reaction conditions to activate C-H bond in propylene are less energy demanding, thus has a positive effect on selectivity.[2] 6. Alkene activation is easy and does not requires severe operating conditions, because they have a high reactivity. [3] 7. Does not necessarily needs a very active, selective and stable catalysts.[3] 8. Products are generally more stable than reactants, and they are not easily
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decomposed during the reaction, thus preventing the formation of undesirable oxygenated C and N compounds.[3] 4.2. 2 Propane Ammoxidation Production of acrylonitrile by propane ammoxidation is a conventional process. By this reaction route, maximum yield and selectivity of 60 to 80 and 40%-50%
[4]
can be obtained.
Propane ammoxidation has a high-conversion (>90%) propane reaction with a yield of 60% acrylonitrile with the aid of mixed metal oxide catalyst which are environmental friendly. Below are the advantages and disadvantage as shown in table 4.3.
Table 4.3: Advantages and disadvantages of propane ammoxidation. Advantages 1. Propane costs were lower than propylene ( 30% less than propylene price).[5] 2. Capital savings (decrease production costs by 20%).[6] 3. Productivity levels comparable to those obtained with propylene. Disadvantages 1. By using propane, need higher costs for excess ammonia and H2SO4 required for ammonia neutralization. 2. Higher capital for waste-water disposal. 3. Alkane activation(limiting step) lead difficult and requires severe operating conditions and very active, selective and stable catalysts. 4. Products are less stable than reactants and they can be easily decomposed during the reaction leading to the formation of undesirable oxygenated C and N compounds. [7] 5. The adsorption rate of propane is near 10 times smaller than that of propylene. [7] 6. The reaction conditions to activate the CH bond in propane are more energy demanding, which has a negative effect on selectivity. 7. The low activity of propane has also led to the use of gas-phase additives (e.g., H2S or CH3Br) as radical generators (environmental concerns do not make this option attractive).
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4. Operation temperatures not higher than 500 C. 5. Maximize co-products formation, such as acetonitrile (ACN) and hydrogen cyanide (HCN) - high value in the chemical market.
4.2.3 Decision Making In summary, the process route selection should be done according to feasibility in term of economic, environment and also technical. By having this as consideration, propylene ammoxidation is the most convenient because the technicality of practicing it has a worldwide acceptance over acrylonitrile producer. Propylene ammoxidation with the best catalyst are able to yields 80-82% of acrylonitrile and the reaction rate is high enough to achieve almost total perpass conversion at ratios of reactants close to stoichiometry. Economic wise, this process route has advantages on the saving operational cost which minimize wastewater treatment and enhance by the value added of the by products produced. Some processes upset were also faced due to inappropriate catalyst consumption and need more sophisticated handling of catalyst. By having greener and economic choice, propylene ammoxidation is the right option for the production of the acrylonitrile.
4.2.4 References [1] Dictionary, T.F., Ammoxidation. (2003). Retrieved on 12 November, from http://encyclopedia2.thefreedictionary.com/ammoxidation [2] Florea, M., Silvy,R. P, Grange, P., Inuence of the reaction conditions on the activity properties of vanadiumaluminiumoxynitride propane ammoxidation catalyst. (2003). Retrieved on 12 November, from http://144.206.159.178/ft/53/202391/14404315.pdf [3] Florea, M., Silvy,R.P, Grange P., Vanadium Based Catalysts for Propane ammoxidation reaction. (2008). Retrieved on 12 November, from http://gwchimie.math.unibuc.ro/anunivch/20051/AUBCh2005XIV14956.pdf [4] Bowswell., C, (1999.The technology Frontier: Alkane Activation Chemical Market Reporter, 20. [5] Kinetics and reaction network in propane ammoxidation to acrylonitrile on vanadiumantimony-aluminum based mixed oxides.Research Article. Publication Date: January 1992 [6] Grasselli, R. K. In Handbook in Catalysis; Ertl, et al., Eds.; Wiley-VCH: Weinheim, Germany, 1997; Vol. V, p 2302. [7] Bowker, M.; Bicknell, C. R.; Kerwin, P. Appl. Catal., A( 1997).Propane AmmoxidationTechnology.Journal of Chem, 159 136-205.
23
CHAPTER 5: PROCESS DESCRIPTION

This report is about RAPID project, which mean the integration processes of the refinery to the end petrochemical product will be covered. In this report, the production of acrylonitrile from sour crude oil will be discussed. The processes are covered four important plants, which are Refinery Unit, Hydro-treating Unit, Fluid Catalytic Cracking (FCC) unit and Acrylonitrile Production Unit. Detail process description of the four plants will be delivered with their specific operating conditions. The simulation of the process for the four plants has been performed in Aspen Plus and detailed Process Flow Diagram has been drawn by using Microsoft Visio 2010.
5.1 PLANT UNIT 1: REFINERY PROCESS DESCRIPTION 5.1.1 Introduction Sour crude oil, which is Basra oil from Iraq is chosen as raw material for refinery plant. As sour crude oil contains thousands of complex components and contaminants, a refinery plant is usually the heart of well-integrated RAPID project with extensive downstream processes as well. The typical refinery plant is made up of 500-900 acres with more than over 500 pieces of equipments and tools, such as reactors, stripping column, atmospheric distillation column, desalter, pump, compressor and accumulator. This section will cover the process flow of the proposed 150,000 barrels per day (bpd) of sour crude oil.
5.1.2 Crude oil (Feedstock) Storage and Inventory As discussed in the section 2.1, the Basra oil feedstock availability is stable and reliable for the future coming years. It has been decided that a feedstock inventory of 45 days will be sufficient to counter market fluctuation of feedstock supply. This translates to an additional figure of 1331,325 metric tons of crude oil stored onsite (or 13.4% of the annual feedstock required). The amount of inventory should be reviewed and adjusted at the end of each operating year as a representation of the markets supply volatility. As a point, a smaller inventory is favorable as it reduces the overall operating risk of the plant. However, this must be balanced out with the reliability of continuous production.
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5.1.3 Process Description (1) Desalting Section As the raw crude oil arriving contains quite a bit of water and salt, it is normally sent for salt removing first, in a piece of equipment called a desalter. Raw sour crude oil usually contains significant amount of water, inorganic salts, suspended solids, and water-soluble trace metals. In refining process, the first step is to reduce these contaminants by desalting (dehydration) so that corrosion, plugging, and fouling of equipment can be avoided and also to prevent poisoning the catalysts in the processing units. Sodium, calcium and magnesium chlorides (NaCl, CaCl2 and MgCl2) are frequently found in crude oil. Presence of these compounds in crude oil can cause several problems in the
0
refining processes, this is because all those salts are hydrolysable at temperatures above 120 C. Upon hydrolysis, the chlorides get converted into hydrochloric acid, which will find its way to the distillation column's overhead where it will corrode the overhead condensers. A good performing desalter can remove about 90% of the salt in raw crude. Intense mixing takes place over a mixing valve and (optionally) as static mixer. The desalter, a large liquid full vessel, uses an electric field to separate the crude from the water
0
droplets. It operates best at 120 - 150 C, hence it is conveniently placed before the preheat train. Desalting units remove contaminants from crude oil by washing water. After the oil is washed and mixed, demulsifying chemicals are added and then the electrostatic fields are used to break the emulsion. About 27% wash water is added to the oil as an extraction agent. Desalter effluent is a combination of many things such as: brine washing water used for removing salt, sand and mud washing water jet used at periodic intervals, connate water produced from the reservoir with crude oil. Desalters wastewater contains oil, demulsifier, and oxygen scavenger
[2]
(2) Pre-Flashing Section Downstream the desalter, crude is firstly heated up a piece of equipment, named as 'preflash vessel', at about 170 C -200 C, and pressure about 2 - 5 barg, where the vapours are separated from the remaining liquid. Vapours are directly sent to the atmospheric distillation column, and by doing so, the hydraulic load on the remainder of the crude preheats train and furnace is reduced, resulting in smaller piping and pumps required. Just upstream the pre-flash vessel, a small caustic stream is mixed with the crude, in order to neutralize any hydrochloric acid formed by hydrolysis. The sodium chloride formed will leave the atmospheric distillation column via the bottom residue stream. The dosing rate of caustic is
25
adjusted based on chloride measurements in the overhead vessel, which is typically around 10 20 ppm [3].
(3) Heat Exchanger Network (HEN) & Furnace After being heated up by pre-flash vessel, the crude needs to be heated up more before entering the atmospheric distillation column and this is done at first in a series of heat exchangers where heat is taken from other process streams which require cooling before being sent to rundown. Heat is also exchanged against condensing streams from the main column. Typically, the crude will be heated up in this way up to a temperature of 200 C - 280 C [3], before entering a furnace. At about 200 C - 280 C, the crude enters the furnace where it is heated up further to about 330 C-370 C. The furnace outlet stream is sent directly to the atmospheric distillation column. Here, it is separated into a number of fractions, each having a particular boiling range.
(4) Physical Separation: Atmospheric Distillation Unit (ADU) Distillation is the crucial step in the processing of crude oil and it takes place in a tall steel tower called a atmospheric distillation column. The inside of the column is divided at intervals by horizontal trays. The column is kept very hot at the bottom (but as different hydrocarbons boil at different temperatures, the temperature gradually reduces towards the top, so that each tray is a little cooler than the one below. The column is designed to be insulated in order to minimize heat loss to the environment, hence energy saving can be achieved. Most of the fractions in the crude oil vaporize and rise up the column through perforations in the trays, losing heat as they rise. When each fraction reaches the tray where the temperature is just below its own boiling point, it condenses and changes back into liquid phase. A continuous liquid phase is flowing by gravity through 'downcomers' from tray to tray downwards. In this way, the different fractions are gradually separated from each other on the trays of the fractionation column. The heaviest fractions condense on the lower trays and the lighter fractions condense on the trays higher up in the column. At different elevations in the column, with special trays called draw-off trays, fractions can be drawn out on gravity through pipes, for further processing in the refinery. At top of the column, vapours leave through a pipe and are routed to an overhead condenser, typically cooled by air fin-fans. At the outlet of the overhead condensers, at
0
temperature about 40 C, a mixture of gas, and liquid naphtha exists, which is falling into an
26
overhead accumulator. Gases are routed to a compressor for further recovery of LPG (C3/C4), while the light naphtha is pumped to a hydrotreating unit for sulfur removal. An atmospheric distillation column needs a flow of condensing liquid downwards in order to provide a driving force for separation between light and heavy fractions. At the top of the column this liquid flow is provided by pumping a stream back from the overhead accumulator into the column. Unfortunately, a lot of the heat provided by the furnace to vaporise hydrocarbons is lost against ambient air in the overhead fin-fan coolers. A clever way of preventing this heat lost of condensing hydrocarbons is done via the circulating refluxes of the column. In a circulating reflux, a hot side draw-off from the column is pumped through a series of heat exchangers, where the stream is cooled down. The cool stream is sent back into the column at a higher elevation, where it is been brought in contact with hotter rising vapours. This provides an internal condensing mechanism inside the column, in a similar way as the top reflux does which is sent back from the overhead accumulator. The main objective of a circulating reflux therefore is to recover heat from condensing vapours. An atmospheric distillation column will have several (typically three) of such refluxes [3], each providing sufficient liquid flow down the corresponding section of the column. An additional advantage of having circulating refluxes is that it will reduce the vapour load when going upwards in the column. This provided the opportunity to have a smaller column diameter for top sections of the tower. Such a reduction in diameter is called a 'swage'. The lightest side draw-off from the atmospheric distillation column is a fraction called
0
kerosene, boiling in the range 160 - 280 C, which falls down through a pipe into a smaller column called 'side-stripper'. The purpose of the side stripper is to remove very light hydrocarbons by using steam injection or an external heater called 'reboiler'. The stripping steam rate is controlled such as to meet the flashpoint specification of the product. Similarly to the atmospheric column, the side stripper has fractionating trays for providing contact between vapour and liquid. The vapours produced from the top of the side stripper are routed back via pipe into the fractionating column [3]. The second and third (optional) side draw-offs from the main fractionating column are
0
gasoil fractions, boiling in the range 200 - 400 C, which are ultimately used for blending the final diesel product. Similar as with the kerosene product, the gasoil fractions (light and heavy gasoil) are first sent to a side stripper before being routed to further treating units. At the bottom of the atmospheric distillation column, a heavy and black coloured fraction called residue is drawn off. In order to strip all light hydrocarbons from this fraction properly, the
27
bottom section of the column is equipped with a set of stripping trays, which are operated by injecting some stripping steam (1 - 3% on bottom product) into the bottom of the column. The atmospheric residue will further send to vacuum distillation column to undergo separation and purification.
*Vacuum distillation process will be excluded in our plant due to time constraints and nonrelated to our final product- Acrylonitrile.
5.1.4 REFERENCES [1] Wall Street Journal, W. Shell & Petronas To Start Drilling At Iraq Majnoon Oil Field In July. (2012). Retrieved 30 October 2012, from http://articlesofinterestkelley.blogspot.com/2011/03/iraq-oil-shell-to-start-drilling-at.html. [2] Pak, A., Mohammadi, Toraj, Wastewater treatment of desalting units. Desalination, 2008. 222(13): p. 249-254. [3] Haslego, C., Refinery-Process-Description. The Chemical Engineer's Resources
5.2 PLANT UNIT 2: HYDRO-TREATING PROCESS DESCRIPTION 5.2.1 Introduction Hydrodesulphurization unit in the plant are responsible for the removal of sulphur as primary target and also other contaminants such nitrogen, heavy metals, saturated olefins and potential of aromatics from light naphtha. Sulphur needed to be removing through hydrodesulphurization because it can lead of corrosion of metal and upset the processes of the raw material ahead. The light naphtha is feed at 20170 kg/hr through the hydrodesulphurization unit with initial sulphur content about 0.05% and produces desulphurized light naphtha with sulphur content less than 5ppmw. The sulphur are removed and captured as hydrogen sulphide.
5.2.2 Process Description (1) Pre-Heater and Furnace [1][2][3] The light naphtha from the refinery is then combined with the hydrogen stream (recycle hydrogen and hydrogen feed) in excess to optimize the desulfurization process. The resulting liquid-gas mixture is preheated through heat exchanger which has it hot stream of reactor outlet stream. The stream is then passed through furnace and further heated to a temperature of 598.15 K.
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(2) Hydrodesulfurization Reactor [4][5] Hydrodesulfurization process is carried out by a fixed bed reactor with the aid of catalyst of cobalt/nickel-molybedenum. The heated stream is passed through the reactor and hydro treating process begins to happen when hydrogen form saturated compound, namely hydrogen sulphide by reacting with unsaturated hydrocarbon. The catalyst bed in the reactor is capable to remove trace of metals and other heavy solids through their packing. This process is described by this reaction: Hydrocarbon-S + H2 Hydrocarbon + H2S This process has a high conversion of hydrogen sulphide at about 90%. The reactor runs at temperature of 598.15 K and pressure of 2026.5 kPa to ensure the partial pressure of hydrogen are sufficient to desulfurize the light naphtha. Due exothermic reaction in the reactor, it lead to a hot product stream and partially cooled by flowing through heat exchanger. (3) Naphtha Stripper [6][7] The purpose of introducing stripping unit is to remove the desulphurized naphtha from the excess hydrogen and hydrogen sulphide. The operating temperature of the stripper is affected on the bubble point of desulphurized naphtha. The partially cooled product stream from the reactor is further cool in the cooler to a temperature of 328.15 K .The reduce in temperature lead the condensation of desulfurized naphtha thus the sour gasses are removed by providing heat through the steam reboiler at 474.15K. The condenses reflux at 323.15K where desulphurized naphtha form liquid and remove to bottom to further process at fluid catalytic cracking unit. The vapour form are primarily sour gasses are removed as top product of the stripper (4) Amine Absorber [8] The amine treating unit removes carbon dioxide (process gas) and hydrogen sulfide from the sour gas and also remove trace amount of hydrocarbon. The amine (methyl-diethanolamineMDEA) is regenerate and recycled in this treating unit. MDEA has a low absorption of carbon dioxide and high absorption of hydrogen sulfide, this encourage a complete absorption of hydrogen sulfide from sour gas. The feed sour gas stream from the stripper enters the bottom of amine absorber, while the cooled lean amine entered the top of the absorber. The feed sour gas flows upward counter-current to the lean amine solution. Rich amine solution with acid gases leaves the bottom of absorber at elevated temperature, due to exothermic absorption reaction.From the top of the absorber, the hydrogen is
29
removed as sweet gas and then compressed through compressor as a recycle stream where it combine with hydrogen make up stream.
(5) Amine Surge Drum The rich amine stream from the bottom of amine absorber then further to amine surge drums and allow separation of hydrocarbon from the amine solution. This surge drum serves as an separation for the hydrocarbon where flare system were attached for safety reason. The hydrocarbon that has been removed from the rich amine stream might be in vapour or liquid phase. The liquid phase are remove with a flow rate less than 10kg/hr and vapour are passed through to flare system where it will be burnt out. (6) Amine Regenerator [9] The amine solution is regenerate and striping of hydrogen sulfide and carbon dioxide takes place. Amine regenerator reboiler supply heat to strip hydrogen sulfide and carbon dioxide from the rich amine by using steam as heating medium. The rich amine stream from the amine surge drum is passing through heat exchanger to be preheated before being feed into amine regenerator. The heat supply by the reboiler steam lead to partial pressure of hydrogen sulphide in the amine drop and enhance the driving force of the hydrogen sulphide gasses move away from the amine. Hydrogen sulphide (acid gasses) vapour leaving the top of the amine generator is cooled in the overhead condenser. The mixture of gasses and condensed liquid stream is passed through reflux accumulator. The accumulator separates the uncondensed gas (acid gas) and trace amount of water will be removed. Condensate (lean amine) is pump back to the amine regenerator through reflux pumps. The lean amine from the amine regenerator is cooled in the heat exchanger and further cooled in the cooler before entering the absorber. Amine make-up stream available for the quick recover of amine for the case of loses happen in the amine regenerator. [1]
5.2.3 References [1] Law D. (August, 1994)."New MDEA Design in Gas Plant Improves Sweetening, Reduces CO2," Oil & Gas Journal, Vol. 92, (No35), p. 83. [2]Distillation Process for Light Gas Oil Hydrodesulfurization., Chemical EngineeringandProcessing , 43(2004), pp1309-1326. [3] Hou, W., SU, H., HU, Y., CHU, J., Modeling, Simulation and Optimization of aWhole Industrial Catalytic Naphtha Reforming Process on Aspen Plus Platform.,Chinese Journal of Chemical engineering, Volume 14, Issue 5, October 2006,Pages 584-591.
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[4] Revamp of NHT&Platformer Unit., Tehran North Refinery, Process Data Book,Volume 1, October 2003, AxensCompany. [5] Breivik, R., Egebjerg, R.: Novel Coker Naphtha Hydrotreating Technology, ERTC 12th Annual Meeting, Barcelona, 19 November, 2007. [6] A.Lengyel, S.Magyar, J.Hancs k. Upgrading of Delayed Coker Light Naphtha in a Crude oil Refinery, Petroleun& Coal Journal, Vol.51(2) p.80-90(2009). [7] S.Sadighi, S.R.S.Mohaddecy, O.Ghabouli, M.Bahmani.Revamp Of Naphtha Hydrotreating Process In An Iranian Refinery, Petroleun& Coal Journal, Vol.51(1) p.45-50(2009). [8] Abry, R.G.F., and M.S. Dupart, "Amine Plant Troubleshooting and Optimization," Hydrocarbon Processing, Vol.74, (No. 4), p. 41 (April, 1995). [9] Bullin, J.A., J.C., Polasek, and J.W. Holmes, "Optimization of New and Existing Amine Gas Sweetening Plants by Computer Simulation," Proceedings of the 60th GPA Annual Convention, p. 142 (1981). 5.3PLANT UNIT 3: FLUID CATALYTIC CRACKING (FCC) PROCESS DESCRIPTION 5.3.1 Introduction Fluid Catalytic Cracking (FCC) has been chosen instead steam cracking because it is able to produce more gasoline with higher octane and less heavy fuel oils and light gases. In this process plant, high yield of propylene is achieved by using the SAPO-11 catalyst in the cracking reaction, not only that, operating condition of the reactor also been lowered. The high yield of propylene is favourable as it is the feedstock for the acrylonitrile production. There are basically three main unit for the FCC plant, which is reactor-regenerator unit, gas membrane separation unit and distillation column purification unit.
5.3.2 Process Description (1) Feedstocks to the Reactor (R-02) There are two streams fed into the reactor (R-02) for undergoing the cracking reaction. The main stream, which is the light naphtha came from the hydro-treating plant and one recycle stream came out from the final distillation column which contains the 99.9% purity of butane. (a) The light naphtha from hydro-treating plant is the desulphurized light naphtha, which consisting the eight components with a negligible small amount of sulphur (less than 0.5ppmw). The list of the components of light naphtha and its mole fraction percentage is shown in Table 1 below.
Table 5.1: Light naphtha composition from the hydro-treating plant. [1] Components Mole fraction (%)
n-Pentane iso-Pentane n-Hexane iso-Hexane
18.71 9.82 17.05 19.39

31
Cyclopentane Methylcyclopentane Cyclohexane Benzene Total
6.45 13.27 9.44 5.87 100.00
The light naphtha stream (Stream Number 58) has the mass flow rate of about 18,358 kg/hr at 474.15 K and 1013.25 kPa. Since the reactor operates at 872 K and 340 kPa, the light naphtha stream (58) is passing through a turbine (P-12) to drive the relieved pressure to achieve the stream (82) at 360 kPa. The power generated is sent to the power regeneration plant that could be used in this FCC plant. After that, stream (83) gains the heat up to 673.15 K through the heat exchanger (Hx-08). The stream (83) is now at 673.15 K and 360 kPa in gas phase.
(b) Recycle stream came out from the final distillation column which contains the 99.9% purity of butene. The bottom stream (99) of the final distillation column contains 99.9% purity of butane at 285.4 K and 200 kPa. The stream (99) passes through a pump (P-16) to increase the pressure to 360 kPa. Then, stream (100) passes through a heat exchanger (Hx-09) to gain heat up to 500 K. However, it (stream 101) is not yet satisfies the requirement operating temperature of the reactor. Thus, another back-up boiler (B-01) is used to heat up the stream (102) up to 872 K and it is in gas phase. Both the stream (83) and (102) are the light naphtha and butene streams respectively, are being mixed in a mixer (M-02) and fed into the riser of the reactor (R-02). (2) Reactor (R-02) 2.1 Riser, Riser Termination Device (RTD) and Cyclone The light naphtha (83) and recycle butene (102) are fed into the riser together with a controlled amount of regenerated catalyst. At the same time, the hot generated catalyst vaporizes the feed, hence the cracking process begins. The endothermic reaction takes place in the riser with the residence time of 2-10s at 872 K and 340 kPa. [2] The resultant vapors carry the catalyst upward through the riser. At the top of the riser, the desired cracking reactions are completed, and the catalyst is quickly separated from the hydrocarbon vapors to minimize secondary reactions. There is a riser termination device (RTD) used to turn the catalyst direction downward. Besides, a cyclone separation unit is installed at the upper part of the reactor and it is used to separate the catalyst from the vapor product. 2.2 Stripping Section and Baffles In additional, the catalyst-hydrocarbon mixture flows back in the disengaging zone. Stripping steam is injected into the bottom of the reactor where there is a stripper section. Stripping stream, at a rate of 2 kg to 5 kg per 1000 kg circulate catalyst is primarily used to remove the entrained hydrocarbons between catalyst particles. The stream used has superficial
32
velocity of 0.75 ft/sec (0.23 m/sec). [3] The oil is removed from the catalyst with the help of some baffles installed in the stripper. After that, the spent catalyst is sent to the regenerator through a standpipe. (3) Regenerator (RG-01) 3.1 Coke Formation and Catalyst Regeneration The coke deposited on the spent catalyst which is produced in the cracking reaction, is burned off in the regenerator at 943.15 K and 700 kPa by introducing excess air to ensure the efficient combustion of coke. The spent catalyst entering the regenerator contains between 0.4 wt% and 2.5 wt% coke, depending on the quality of the feedstock. Components of coke are carbon, hydrogen and trace amounts of sulfur and nitrogen. This burn according to the following reactions:
[3]
C + O2 CO CO + O2 CO2 C + O2 CO2 H2 + O2 H2O S + xO SOx N + xO NOx Air provides oxygen for the combustion of coke and is supplied by one or more air blowers. The air blower provides sufficient air velocity and pressure to maintain the catalyst bed in a fluid state. The air enters the regenerator through an air distributor located near the bottom of the vessel. The air distributor is important in achieving efficient and reliable catalyst regeneration. During regeneration, the coke level on the catalyst is typically reduced to 0.05%. [3] 3.2 Two-Stage Cyclones There is a high efficiency two-stage cyclones separator used to separate the remaining catalyst from the hot flue gas. After that, the hot flue gas produced will be exiting at the top of the regenerator. The hot flue gas contains carbon dioxide, carbon monoxide, water and excess air at the regenerator temperature. Therefore, the hot flue gases are sent to the power recovery unit to produce superheated steam. 3.3 Standpipe/ Slide Valve From the regenerator, the regenerated catalyst flows down a transfer line which is a regenerator standpipe. The standpipe provides the necessary pressure to circulate the catalyst around the FCC unit. A slide valve is used to regulate the flow rate of the regenerated catalyst to the riser. Its main function is to supply enough catalyst to heat the feed and achieve the desired reactor temperature. The regenerated catalyst flow is mainly controlled by adjusting the pressure differential between the reactor and regenerator.
33
(4) MFI Zeolite Membrane (Remove H2) The vapor stream (89) is produced from the catalytic cracking reaction which containing the around 77% of propylene, 5% of ethylene, 14% of butene and 2% of hydrogen. This stream is further purified by using MFI zeolite membrane and subsequently two distillation columns in order to get the highest purity of propylene. The operating conditions for the MFI (Mordenite framework inverted) zeolite membrane is at 773.15 K and 168 kPa. [5] Therefore, stream (89) which is at 872 K and 340 kPa needs to be cooled down and reduced pressure to achieve the desired temperature and pressure. The pump (P-14) is used to relief the unwanted pressure and the heat exchanger (Hx-09) is used to exchange the unwanted heat to another stream. The pressure relieved is used to drive a turbine for the power generation network that could be used in this FCC plant. Based on few literature reviews, Dong J. et. al. has concluded that at high temperatures (500 C or 773.15 K), the MFI zeolite membrane becomes permselective for hydrocarbon over hydrogen. [5] Besides, Pan M. et. al. has concluded that the secondary-grown MFI zeolite membrane prepared with template is impermeable to C3 and C4 hydrocarbons. [6] Based on Sigma Aldrich, the crtical diameter of the molecules of hydrogen, propylene, ethylene and butene are 2.4 , 5 , 4.2 and 5.1 respectively. Obviously, the molecule size for hydrogen is smaller than all the propylene, ethylene and butene molecules. Therefore, an assumption is made, saying that about 99.9% of hydrogen is being permeated through the MFI zeolite membrane over the propylene, ethylene and butene. The stream (92) contains the 99.9% purity of hydrogen sent to hydrotreating plant for the process use. All the propylene, ethylene and butene are sent for further purification unit. (5) Distillation Column I (Remove Ethylene) The retentate, stream (93) is sent for further purification by using two distillation columns. Before that, stream (93) passes through pump (P-15) to increase pressure from 168 kPa to 1800 kPa. Then, stream (94) passes through heat exchanger (Hx-08) to be removed the heat and cooled down to 298.15 K. Stream (95) enters the first distillation column at the 8 th feed stage. The operating condition of the first distillation column (D-02) is tabulated in the Table 3 below. The upper stream (96) comes out with 99.6% purity of ethylene at 245.3K and 1800 kPa in gas phase, which is then stored and sold. The bottom stream (97) comes out from the D-02 will then enters another distillation column to achieve the desire purity of the desired product, which is propylene.
Table 5.2: Requirement conditions of the first distillation column (D-02).
Distillation Column1 (D-02) Number of stages 56 Feed stage 8 Reflux ratio 0.99 Distillate to feed mole ratio 0.242 Condenser type Partial Condenser Pressure 18 bar Reboiler Pressure 12 bar
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(6) Distillation Column II (Remove Butene) Stream (97) enters the second distillation column (D-03) at the 8th feed stage. The operating condition of the second distillation column (D-03) is tabulated in the Table 4 below. The upper stream (98) comes out with the desired product of 97.6% purity of propylene at 289.5 K and 850 kPa. Whereas, the bottom stream (99) contains 99.9% purity of butene at 285.4 K and 200 kPa, which is then recycled back to the reactor (R-02) for further cracking reaction into smaller hydrocarbon.
Table 5.3: Requirement conditions of the second distillation column (D-03).
Distillation Column2 (D-03) Number of stages 35 Feed stage 8 Reflux ratio 0.6 Distillate to feed mole ratio 0.867 Condenser type Partial Condenser Pressure 8.5 bar Reboiler Pressure 2 bar 5.3.3 Catalytic Cracking Reaction The fluid catalytic cracking takes place on the heterogeneous catalyst and it is realized in the sorbed phase, where the acid sites, on the catalyst surface, assist in the formation of and determine the type of reactions undergone by ionic intermediary species, carbonium ions. [16] Figure 2 below shows the reaction routes of carbonium ion in n-Paraffin catalytic cracking. [17]
Figure 5.1: The reaction routes of carbonium ion in n-Paraffin catalytic cracking. [17]
35
Lets consider the cracking of normal paraffin. In the first step of reaction, the intermediate product, carbonium ion is formed. According to modern theories, acidic sites of the Bronsted (*H+) or the Lewis (*) type, which is strongly deficient in electrons, may stabilize one of the hydrogens of the paraffin molecule in the form of hydride ion (H -), with the formation of the complementary carbonium ion from the hydrocarbon: [16]
Since C-H bond is covalent, its ionization is, on energy considerations, not favored and can only take place on very efficient acidic sites. The carbonium ion, once formed on the catalyst surface, may react in various ways. [16] The Primary Cracking Reaction is the heterolytic cleavage of the C-C bond, located in position to the positive charge, with formation of an olefin and a new carbonium ion: [16]
The primary carbonium ion form is very unstable and undergoes an internal rearrangement by migration of a hydrogen atom (hydride transfer), with formation of a more stable secondary or even tertiary carbonium ion: [16]
It may happen also isomerization of the carbon chain according to the reactions: [16]
Alternatively, they may extract a hydride ion from a molecule in the feed and produce a paraffin and a new carbonium ion: [16]
By referring to the journal written by Wang F. et. al. that had been published in the Chemical Engineering and Processing 49 (2010) 51-58, there are about 38 reaction involve in the cracking process.[15] However, assumption is made for the simplification of the FCC process in this RAPID plant. The reactions involve in the FCC process in this plant are:
36
No. 1 2 3 4 5 6 7 8 9 10 11
Reaction Equations Light nathpha xC3H6 + yC2H4 + zC4H8 + wH2 C2H6 C2H4 + H2 C2H4 + H2 C2H6 C2H2+ CH4 C3H6 C2H4 + C2H6 + C3H6 + CH4 C3H8 C3H6+ H2 C3H6 + H2 C3H8 C3H8 C2H4 + CH4 C3H8+ C2H4 C2H6 + C3H6 C3H4 + H2 C3H6 C4H6 + H2 C4H8
5.3.4 Justification of Catalyst Used (1) SAPO-11 Catalyst [used in the Reactor (R-02)] The silicoaluminophosphates (SAPO) molecular sieve has a network of AlO4, SiO4 and PO4 tetrahedra linked by oxygen atoms. The negative charge in the network is balanced by the inclusion of exchangeable protons or cations such as alkali or alkaline earth metal ions. The interstitial spaces or channels which are formed by the crystalline network enable SAPOs to be used as molecular sieves in separation processes and in catalysis. [13] In accordance to Advanced Chemicals Supplier Material [14], SAPO-11 has a linear formula (SiO2)x (Al2O3)y (P2O5)z . The technical parameters have been shown in the table 5 below.
Table 5.4: Technical parameters of SAPO-11 by the ACS Material. [14]
Appearance Specific Surface Area (m2/g) Pore Volume (cm3/g) SiO2 (%) Al2O3 (%) P2O5 (%)
White Powder 180 0.16 ~6 ~ 48 0.2
There are few patents writing about the using of SAPO catalyst to increase the propylene production. According to Chen. T.J. et. al. (U.S. Pat. No. 6,429,348 B1), they have come out a patent about the invention of using silicoaluminophosphates (SAPO) catalyst under catalytic cracking conditions for converting an olefinic hydrocarbon feedstock to propylene. The catalyst has enhanced stability as used when treated with a rare earth metal or metals in a concentration effective to provide a catalyst which exhibits a higher conversion of a hydrocarbon feedstock to propylene than an equal quantity of an untreated sample of the same catalyst under the same conditions. [13]
37
Since there is large volume of production of olefins, small improvements in operating efficiency translate into significant profits, catalyst play an important role in more selective conversion of hydrocarbons to olefins. Non-zeolite molecular sieves such as silicoaluminophosphates (SAPO) catalyst including those describe in U.S. Pat. No. 4,440,871 also provided excellent catalysts for cracking to selectively produce light hydrocarbons and olefins. Chen. T.J. et. al. (U.S. Pat. No. 6,429,348 B1) has done the experiment to compare the performance of catalyst in the catalytic cracking reaction between the ZSM-5 and SAPO-11. Results have proven that SAPO-11 produced significantly more propylene and less ethylene and butene than ZSM-5 catalyst. SAPO-11 was found to be very selective for propylene with propylene selectivity of 64% and low production of both ethylene and butene. The conversion of using SAPO-11 is 89.8. [13] In addition, the most preferably catalytic cracking conditions are in the temperature range of 500C-650C (773.15 K-923.15 K). Pressure in the contact zone may be from 0.1 atm-30 atm (10.13 kPa-3039.75 kPa), and preferably 1-3 atm (101.33 kPa-303.98 kPa). [13]
(2) MFI (Mordenite framework inverted) Zeolite [used in the Gas Membrane (G-01)]
Zeolite is crystalline microporous aluminosilicate materials with a regular three dimensional pore structure, which are thermal and chemical stabilities. Therefore, it is suitable to be used in this plant, as the high temperature required in the gas membrane separation, which is 773.15 K. The MFI zeolite has the pore size 0.55 nm and adsorption properties favorable for the separation of such gases. [5] MFI type zeolite membranes have very good permeation and separation properties. Due to their molecular sieve function, zeolite membranes can principally discriminate the components of gaseous or liquid mixtures dependent on their molecular size. [9] Characterization of zeolite membranes is of great importance and among various techniques, gas permeation is a non destructive characterization techniques that allow the separation capability and the molecular transport phenomena. Moreover, the study has shown that good separation performances of high quality MFI-zeolite membranes through a standard reliable and reproducible characterization procedure using hydrocarbonaceous mixtures at high temperatures.
[12]
Zeolite is widely used in various hydrocarbon processing operations. [10] Besides, it is also used at industrial scale for gas separations, for example in the field of gas treatment, refining and petrochemistry. [12]
38
5.3.5 REFERENCES [1]Light naphtha composition. Retrieve 30 September 2012, from http://www.ripi.ir/index.php?option=content&task=view&id=65 [2]Fahim M.A., Alsahhaf T.A & Elkilani A. (2009). Fundamentals of petroleum refining. 1 st ed. Elsevier Science; UK. [3]Sadeghbeigi R. (2000). Fluid Catalytic Cracking Handbook. Design, operation and troubleshooting of FCC facilities. 2nd ed. Butterworth-Heinemann; United States of America. [4]Hemler C.L. & Smith L.F. Handbook of Petroleum Refining Processes. Chapter 3.3 UOP Fluid Catalytic Cracking Process. [5]Dong J.H., Lin Y.S. & Liu W. Multicomponent hydrogen/ hydrocarbon separation by MFIType zeolite membranes. [6]Pan M. & Lin Y.S. Template-free secondary growth synthesis of MFI type zeolite membranes. Microporous and mesoporous material 43 (2001) 319-327. [7]Eldridge R. B. Olefin/ paraffin separation technology: a review. Ind. Eng. Chem. Res. 1993, 32, 2208-2212. Phillips Petroleum Company, Bartlesville, Oklahoma. [8]Coleman S.T., Sawyer G.A. & Bridges R.S. et. al. Production of 1-butene and propylene from ethylene. United States patent, Pub. No. US 20120095275A1. [9] Masuda T., Fukumoto N. & Kitamura M. et. al. Modification of pore size of MFI-type zeolite by catalytic cracking of silane and application to preparation of H2 separating zeolite membrane. Microporous and mesoporous materials 48 (2001) 239-245. [10]Kang Li. (2007) Ceramic membranes for separation and reaction. John Wiley & Sons, Ltd: UK. [11]Keady G.S., Puerto J. & Garbouchian B. Cat cracker gas plant process for increased olefins recovery. United States patent, Pub. No. US 20010044565A1. [12]Chau C., Sicard M. & Terrasse P. et. al. Highly selective MFI-zeolite membranes for hydrocarbon separations. [13]Chen T. J., Davis S.M & Martens L.R.M et. al. Method for selectively producing propylene by catalytically cracking an olefinic hydrocarbon feedstock. [14]Sapo-11. Advanced Chemicals Supplier Material. Retrieve 14 November 2012, from http://www.acsmaterial.com/product.asp?CID=70&ID=78 [15]Wang F., Xu Y.Y & Ren J. et. al. Experimental investigation and modeling of steam cracking of Fischer-Tropsch naphtha for light olefins. Chemical engineering and processing 49 (2010) 51-58. [16]Decroocq D. Catalytic Cracking of Heavy Petroleum Fractions. [17]Ishihara A., Inui K., Hashimoto T. & Nasu H. Preparation of hierarchical and Y zeolite containing mesoporous silica-aluminas and their properties for catalytic cracking of ndodecane. Journal of Catalyst 295 (2012) 81-90. [18]Molecular Sieves. Retrieve 1 December 2012, from http://chem.chem.rochester.edu/~nvd/molecularsieves.html
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5.4 PLANT UNIT 4: ACRYLONITRILE PRODUCTION PROCESS DESCRIPTION 5.4.1 Introduction Acrylonitrile (ACN) is one of the leading chemicals with a worldwide production of about 5.5 million tonnes in 2012, with total acrylonitrile demand in 2018 is forecast at 6.516 million tonnes[4]. In this project the target plant capacity is 120 000 ton/yr, corresponding to a reactor production of 272.29 kmol/h or 14 448.68 kg/h acrylonitrile polymer 95% grade purity. Accordingly, the propylene feed is 340 kmol/h. About 90% of the worldwide acrylonitrile (ACN) is manufactured today by the ammoxidation of propylene, as described by the reaction below: CH2=CH-CH3 +NH3 + 3/2O2CH2=CH-CN+ 3H2O
5.4.2 Process Description (1) Reaction: Propylene Ammoxidation The ammoxidation reaction is carried out in a fluidized bed reactor (R-03). Propylene (chemical grade) is transferred from its respective liquid storage tanks and vaporized in HX-10 against the hot water from the downstream reboiler. Air is adiabatically compressed in a centrifugal compressor (C-02) that is driven by a high pressure (HP) steam turbine (P-25) and is introduced at the bottom of the reactors. Ammonia is being transported into reactor in gaseous phase. [4]
BFW: Boiler Feed Water Gas: Product Gas
Figure 5.2: Sketch of fluid-bed reactor for acrylonitrile synthesis. The optimal catalyst (Bismuth-Molybdenum Oxide) particles[2] size is in the range 40 to 100 m, in which the presence of a certain amount of fines is necessary for ensuring homogeneous fluidization. The gas velocity is slightly above the minimum, in general between 0.4 to 0.5 m/s[2]. Trays or screens, usually between 5 and 15, can be placed transversally in order to reduce the negative effect of back mixing. Residence time in the reactor is between 2 to 20s, with an optimal range between 5 to 10s. Longer residence time gives more by-products.
40
(2) Quenching and Adsorbing Section The hot reactor product is cooled to 220 C in an exchanger (E-07). Further cooling is carried out in a direct contact quench cooler (Q-01), which is a column packed with 1 inch pall rings. The quench water is fed at the top and the hot gases are introduced at the bottom. The aqueous stream from the column leaves at 66 C and is sent to waste treatment. The vapour stream from the column, at 80 C , is cooled down to 30 C against cooling water in exchanger E-08 before being contacted with water in the adsorber column (AD-01). The absorber is also a packed column with 1 inch pall rings. The vapour is fed at the base of the column and the water for adsorption is fed to the top of adsorber. The aqueous extract from the column is fed to the acrylonitrile purification section; the unabsorbed gases (stream 113) are further separate out carbon dioxide and sell to third party, for example Mox-Linde as one of our efforts in ensuring our process are environment friendly. This is because there is large amount of carbon dioxide (4700 kg/hr) being emitted into atmosphere, as it will cause air pollution and global warming. The quench cooler and absorber combination are designed to operate at conditions that minimize the loss of valuable acrylonitrile in the quench liquid effluent to waste treatment (stream 109) and the distillation column effluent to incineration (stream 117).
Amine scrubbing is illustrated at PFD 4. Flue gas from the Flash Separator
(F-01)
contains mostly nitrogen and carbon dioxide is sent to a vessel called an absorber (Ad-2). Amine liquid in the absorber flows down over packing and mixes with the flue gas from the combustion process. Carbon dioxide forms a weak chemical bond with the amine and is absorbed into the amine. Nitrogen exits through the top of the absorber and is sent to the stack. Amine rich in carbon dioxide is sent to a vessel called as stripper. Steam is added to the stripper to provide the energy needed to break the chemical bond between the carbon dioxide and the amine. Once the carbon dioxide is stripped from the amine it flows out the top of the stripper where it is dried and compressed into a liquid prior to storage. The amine at the bottom of the stripper is lean in that is contains very little absorbed carbon dioxide. This lean amine is recycled back to the absorber to be used again.
(3) Acrylonitrile Separation High selectivity in acrylonitrile remains a challenge. Today the best separation in adsorber only can give separate acrylonitrile into (40:60), which means that 40% of acrylonitrile goes to
41
Hydrogen Cyanide (HCN) separation, while 60% of acrylonitrile goes to Acetonitrile (AN) separation. The boiling point of acrylonitrile and acetonitrile is very close, hence the use of water as an extractive solvent facilitates the separation of acrylonitrile from acetonitrile [2]. As a result, a crude acrylonitrile (94% purity) stream is separated overhead as a vapour phase and acetonitrile is removed as an aqueous sidestream below the feed tray. To minimize acrylonitrile carryover, the sidestream is cooled in condenser, passing though a decanter (D-01) and decanted, and the organic layer is recycled back to the column. The extractive water to the column consists of a recirculating stream that is withdrawn a few trays from the bottom of column (V-11) and returned back to the top of the column (V-10) via the exchanger (Hx-10, referred to PFD 4) .Thus, the feed to the column is heated against the recirculating water stream; as a result, the extractive water is cooled to 54 C. The heat exchanger is performing the energy saving analysis. The aqueous sidestream is fractionated in column V-11 to produce an enriched acetonitrile. Hydrogen cyanide and remaining 40% acrylonitrile are being separated in column V-08. Due to its toxicity, hydrogen cyanide is usually consumed at its site of production. It will sent to Basf plant for further processing into adiponitrile (refer to chapter 3). Acrylonitrile separated with 97% purity will mixed with 94% purity acrylonitrile, and finally send to storage tank (ST-02). The temperature of the stream after mixed (139) is around 305 K, which does not provide enough energy for reaction to occur. Hence, it is logical for industry to mix two different purities product into a storage tank, provided the activation energy does not exceed.
5.4.3 REFERENCES [1] PCI , A.L., <PCI Acrylonitrile Supply Demand Report 2009 B.pdf>. 2009. [2] Prof. Alexandre C. Dimian, P.C.S.B., Chemical Process Design: Computer-Aided Case Studies. 2008: Wiley.
5.5 PROCESS FLOW DIAGRAM (1) REFINERY (2) HYDRO-TREATING (3) FLUID CATALYTIC CRACKING (FCC) (4) ACRYLONITRILE PROCESS
42
5.5 PROCESS FLOW DIAGRAM (1) REFINERY
43
(2) HYDRO-TREATING
44
(3) FLUID CATALYTIC CRACKING (FCC)
45
(4) ACRYLONITRILE PROCESS
46
CHAPTER 6: MASS AND ENERGY BALANCE

6.1 MASS BALANCE 6.1.1 Introduction According to Felder and Rousseau (2005), the design of a new process or analysis of an existing one is not complete until it is established that the inputs and outputs of the entire process and of each individual unit satisfy balance equations. The law of conservation of mass is introduced, which states that mass can neither be created nor destroyed. [1] A conserved total mass balance or component mass balance in a system either in a single process unit or an entire process can be expressed as below: Input + generation output consumption = accumulation -----------------------------------------------(1) The mass balance table for the refinery, hydro-treating and FCC plants are shown in the Chapter 10 Appendix. Due to the time constraint, only the Aspen Plus values for the mass balance of the three plants are performed. Below part will be focused on the acrylonitrle production plant. 6.1.2 Mass Balance for Reactor For the system with reaction (example: in a reactor), one of the ways to determine the molar flow rates is to build the equations for each components flow rate in terms of extent of reaction. Extent of reaction is a quantity that defines to what degree a reaction has proceeded and has the same unit as the molar flow rate. Once it is found for a particular reaction, the flow rate of every species involved in the reaction can then be calculated. It can be defined as the following = + ------------------------------------------------------------------------------------------------------(2) Where : Outlet molar flow rate of species i : Inlet molar flow rate of species i : Stoichiometric coefficient of species i : Extent of reaction Besides, chemical reactions do not take place instantaneously, but indeed rather slow reaction occurs. It is not practical to design the reactor for complete conversion of the limiting reactant. **Hand calculation of the mass balance for reactor is attached in the Chapter 10 Appendix. 6.1.3 Assumptions Made The possible assumptions that have been made to ease the hand calculation of mass balance and performed in Table 6.1 below. Table 6.1: Assumptions for the calculation of material balance. Unit Assumptions Operation Fluid Bed The last reaction (5th reaction) is negligible due to very low value of the Reactor , Rfractional conversion.
47
03 Absorber Ad-01
Flash Separator F-01
Absorber Ad-02 Ammonia Stripper V-07 HCN Stripper V-08 Water Stripper V-09 Acrylonitrile Stripper V-10 Acetonitrile Stripper V-11 Amine Stripper V-12
All propylene, ammonia, oxygen, nitrogen, HCN and carbon dioxide are recovered to the top products. 40% ACN and 2% AN in the top product stream. All water is recovered to the bottom products. 98% AN and 60% ACN are in the bottom products stream. The recovery of nitrogenin distillate is 98.9% and the recovery ofAcrylonitrile in bottom stream is 99.5%. All oxygen and carbon dioxide will go out as distillate since the boiling point is lower than operating temperature. All hydrogen cyanide will remove as bottom since the boiling point is higher than operating temperature. The recovery of Nitrogen at top is99.9% and the recovery ofcarbon dioxidein bottom stream is 99.9%. The recovery of Ammoniain distillate is 95.9% and the recovery ofAcrylonitrilein bottom stream is 99.9%. All Hydrogen cyanide willgo out as bottom product since the boiling point of HCN is higher than boiling point of light key. The recovery ofHydrogen cyanidein distillate is 96% and the recovery of in Acrylonitrile bottom stream is 99.9%. The recovery of Acrylonitrile in distillate is 99.9% and the recovery of water is 94% in bottom stream. All other component will go out as distillate since the boiling point is less than operating temperature. The recovery of Acrylonitrile in distillate is 99.3% and the recovery of wateris 99.5% in bottom stream. All Acetonitrile will go out at bottom as the boiling point is higher than operating temperature. The recovery of Acetonitrile in distillate is 99.3% and the recovery of wateris 99.7% in bottom stream. The recovery ofCarbondioxide in distillate is 99.5% and the recovery of wateris 99.4% in bottom stream.
6.1.4 Deviation between Manual Calculation and Aspen Results The inlet and outlet mass flow rate of each unit operation in the petrochemical plant of acrylonitrile is shown in the table below. Table 6.2 Inlet and outlet mass flow rate and deviation. Absorber AD-01 Overhead Product Stream Mass Flow Rate of Outlet (kg/hr) Mass Flow Rate Component Deviation (%) Hand Aspen of Inlet (kg/hr) Calculation Plus Propylene 226.39 226.39 216.97 4.16
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Ammonia, NH3 2681.88 Oxygen, O2 141.60 Nitrogen, N2 72352.00 Hydrogen cyanide 909.02 Carbon dioxide 5211.22 Acrylonitrile 14540.56 Acetonitrile 609.59 Bottom Product Stream Component Water, H2O Acrylonitrile Acetonitrile
2681.88 141.60 72352.00 909.02 5211.22 5816.22 12.19
3197.34 181.01 72386.83 934.56 4803.23 5916.39 10.11
19.22 27.83 0.05 2.81 7.83 1.72 17.06
Mass Flow Rate of Outlet (kg/hr) Mass Flow Rate Hand of Inlet (kg/hr) Aspen Plus Calculation 19236.17 19236.17 19801.90 14540.56 8736.34 8625.15 609.59 597.40 429.56
Deviation (%) 2.94 1.27 28.10
Flash SeparatorF-01 Overhead Product Stream (104) Mass Flow Rate Component of Inlet (kg/hr) Oxygen 761.57 nitrogen 72386.83 Acrylonitrile 5928.36 Hydrogen 743.98 cyanide Carbon dioxide 4803.22 Bottom Product Stream (105) Mass Flow Rate Component of Inlet (kg/hr) Oxygen 761.57 nitrogen 72386.83 Acrylonitrile 5928.36 Hydrogen 743.98 cyanide Carbon dioxide 4803.22 Absorber AD-02 Overhead Product Stream (140) Mass Flow Rate Component of Inlet (kg/hr) Nitrogen 72314.44 Carbon dioxide 4803.22 Amine 1108 Bottom Product Stream (141) Mass Flow Rate Component of Inlet (kg/hr) Nitrogen 72314.44 Carbon dioxide 4803.22 Amine 1108
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 761.57 760.44 72314.44 72276.58 29.64 34.06 0.00 61.19 4803.22 4714.01
Deviation(%) 0.14 0.05 14.9 1.85 Deviation(%) 4.9 0.07 8.22 -
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 0.00 1.12 116.05 110.32 5898.71 5894.30 743.98 682.79 0.00 89.22
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 73000.92 72276.58 74 76.45 0 35.78 Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 4.7 4.83 4699.9 4714.01 1108 1072.22
Deviation(%) 1.0 2.7 Deviation(%) 2.76 0.3 3.22

49
Amine Stripper V-12 Overhead Product Stream (142) Mass Flow Rate Component of Inlet (kg/hr) Carbon dioxide 4699.9 Amine 1108 Bottom Product Stream (144) Mass Flow Rate Component of Inlet (kg/hr) Carbon dioxide 4699.9 Amine 1108 Ammonia Stripper V-07 Overhead Product Stream (107) Mass Flow Rate Component of Inlet (kg/hr) Ammonia 524.89 Acrylonitrile 5894.30 Hydrogen 682.79 cyanide Bottom Product Stream (108) Mass Flow Rate Component of Inlet (kg/hr) Ammonia 524.89 Acrylonitrile 5894.30 Hydrogen 682.79 cyanide HCN StripperV-08 Overhead Product Stream (110) Mass Flow Rate Component of Inlet (kg/hr) Acrylonitrile 5894.30 Hydrogen 650.87 cyanide Bottom Product Stream (111) Mass Flow Rate Component of Inlet (kg/hr) Acrylonitrile 5894.30 Hydrogen 650.87 cyanide
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 4676.5 4644.78 55.4 57.34 Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 53.5 55.22 1052.6 1050.23
Deviation(%) 0.6 3.78 Deviation(%) 3.21 0.24
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 524.36 524.89 35.86 0.00 0.00 31.9203343
Deviation(%) 0.1 -
Deviation(%) 0.61 4.67
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 5.89 4.31 624.18 650.87
Deviation (%) 26.0 4.27 Deviation (%) 0.09 -
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 5888.40 5893.98 26.68 0.00
Water StripperV-09 Overhead Product Stream (113) Mass Flow Rate Mass Flow Rate of Outlet (kg/hr) Component of Inlet (kg/hr) Hand Calculation Aspen Plus Water 19805.53 1188.33 1470.32
Deviation (%) 23.7

50
Acrylonitrile 8613.17 Acetonitrile 430.59 Bottom Product Stream (114) Mass Flow Rate Component of Inlet (kg/hr) Water 19805.53 Acrylonitrile 8613.17 Acetonitrile 430.59 Acrylonitrile Stripper V-10 Overhead Product Stream (117) Mass Flow Rate Component of Inlet (kg/hr) Water 171470.32 Acrylonitrile 8613.17 Acetonitrile 430.59 Bottom Product Stream (122) Mass Flow Rate Component of Inlet (kg/hr) Water 171470.32 Acrylonitrile 8613.17 Acetonitrile 430.59 Acetonitrile Stripper V-11 Overhead Product Stream (124) Mass Flow Rate Component of Inlet (kg/hr) Water 170880.96 Acetonitrile 380.13 Bottom Product Stream (125) Mass Flow Rate Component of Inlet (kg/hr) Water 170880.96 Acetonitrile 380.13
8604.55 430.59
8613.17 430.59
0.1 Deviation (%) 1.51 -
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 857.35 789.36 8552.87 8554.68 0.00 50.465 Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 170612.96 170880.96 60.3 58.48 430.59 380.13
Deviation (%) 7.9 0.02 Deviation (%) 0.15 3.33 11.6
Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 512.67 402.5 377.46 379.418 Mass Flow Rate of Outlet (kg/hr) Hand Calculation Aspen Plus 170368.28 170478.74 2.66 1.713
Deviation (%) 21.4 0.51 Deviation (%) 0.06 14.6
6.1.5 Discussion on Deviation For the reactor the deviation is due to reaction occurs and greatly depends on the temperature of system. Oxygen and ammonia amount need to in excess amount in order to react with propylene completely to produce acrylonitrile, and propylene is the limiting reactant. However, in the real situation, the temperature varies in the reactor, covering from low to high temperature. Hence, the conversion of both reactants may be limited by the variable temperature profile within reactor. Moreover, the reactor model that we used in Aspen is RStoic. It is based on the known fractional conversion or extents of reaction, where fractional conversionis a function of time and temperature [X=X (t, T)] [2], but varies temperature profile make the conversion becomes unstable.
51
For the stripper/separator the deviation are mainly because of the model used in the Aspen. Those model did not take some consideration as initial assumption such vapor pressure is depended on temperature only instead considering as non-ideal behavior. Through hand calculation the contact between the components with the tray types with number of tray at high reflux ratio is negligible but Aspen take that into consideration. In overall the deviation in mass balances are accepted since the required purity of acrylonitrile production is obtained same as the hand calculated. The small deviation account from the hand calculation is considerably accepted.
6.2 ENERGY BALANCE 6.2.1 Introduction From the First Law of Thermodynamics[1]: Rate of Energy in- Rate of Energy out+ Rate of Energy Generation- Rate of Energy Consumption = Rate of Energy Accumulation For heat transfer, the equation can also be expressed as: = H + + -------------------------------------------------------------------------------(3) Where, Q: Rate of Heat Transfer W: Rate of Work Transfer H: Changes in enthalpy Ek: Changes in kinetic energy Ep: Changes in potential energy For an open system, the shaft work, change in kinetic and potential energy is negligible. Hence, the energy balance is reduced to: Q= Hrxn = nout Hout nin Hin -------------------------------------------------------------------(4)
To facilitate the energy balance calculations, general assumptions are made: 1. All streams are flowing in steady state condition. 2. Uniform physical conditions along each stream. 3. Negligible shaft work, kinetic and potential energy change. 4. There is no reaction occurs in heat exchanger, pump, compressor, mixer, splitter and distillation column. 5. There is no heat loss to the surrounding.
52
Heat Capacities To calculate the heat duty of each unit operation, the equation used is = To calculate the value of , For ideal gas [1], =
2 1
() -------------------------------------------------------------------------------------------(5)
2 () 1
For solid or liquid, = + ----------------------------------------------------------------------------------(6)
Hence, the most important thing in the calculation is to obtain the Cp value of each component. The specific enthalpy of each component is obtained using ASPEN Properties 11.1 and Perrys Chemical Engineers Handbook 8th Edition (Chapter 2, page 165-170). Cp value of each component was tabulated in Table 6.3 below.
After the specific heat capacity of the component has been obtained, the average enthalpy of the stream can be found by knowing the composition of the component in each stream. = 1 1 + 2 2 + 3 3 + + ------------------------------------------------------(7)
Then, the enthalpy difference between the inlet and outlet stream can be calculated by using the equation as shown below: = -----------------------------------------------------------------------(8) is thus the duty of each unit operation. Table 6.3: Heat Capacities of Components[3] . Name of components Acrylonitrile (ACN) Acetonitrile (AN) Acrolein Ammonia Carbon Dioxide Hydrogen Cyanide (HCN) Nitrogen Oxygen Propylene Water Heat capacity [J/(kmol.K)] 10E-05 1.2271 0.9713 1.5801 4.1847 1.6603 0.7105 0.7960 0.9066 0.9208 0.7615
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6.2.2 Energy Balance for Reactor (R-03) The operating temperature and operating pressure of reactor R-03 is 380 C and 2.2 bar respectively. Assumptions and Considerations: The calculations were done based on following basis assumptions and considerations: 1. Isothermal conditions. 2. Side reactions are negligible. 3. Reaction kinetics is controlled. 4. Conversion of reaction is 80.6%. 5. All streams are in steady state. 6. No heat loss to the surrounding. 7. Liquid phase behaves as an ideal solution. 8. Heat of mixing is negligible compared to heat duty of unit operation. **Hand calculation of the energy balance for Reactor (R-03) is performed in the Chapter 10 Appendix.
Result obtained, Hand Calculation, Q= -189212MJ/hr Aspen Calculation, Q= -191973.53 MJ/hr Percentage of deviation (%) = 1.46 %
Discussion on Deviation (Reactor-R-03) The deviation is due to the neglect of side reactions. Theoretically, there are 4 side reactions where their conversions are low, between 0.027-0.15. The significance of reaction is depending on the temperature inside the reactor, for example, at lower temperature, Reaction 2 is very important and Reaction 3 is negligible; at higher temperature, Reaction 3 is competitive, but Reaction 2 becomes less important. This is because based on the reaction rate expression, it is noticeable that the exp term in the numerators in Reaction 2 and 3 are quite different. Reaction 2 has exp (27000/RT), which means it will decrease when T increases. But Reaction 3 has exp (580/RT). The rate will increase with increasing T. However, in the real situation, the temperature varies in the reactor, covering from low to high temperature. Therefore, we must consider all the side reactions in real case. In Aspen Plus 11.1, six reactions are included in the calculation of energy balance of reactor. Hence, deviation exists between hand calculation and Aspen.
54
6.2.3 Deviation between Manual Calculation and Aspen Results Table below shows the deviation between the manual calculation and the Aspen results. Table 6.4: Heat Duty for each Unit Operation. Sym bol Heat Duty Manual Calculatio n (MJ/hr) -1.89E+07 -19262 26656 30666 106401 9866 -9641 10580 -8143 62746 56354 78780 -18889 73720 -8285 -9696 2.43 2.16 5.81 230 ASPEN Result (MJ/hr) -191973 -17835 36514 31292 92523 10842 -9359.99 9446 -9360 59758 52064 83808 -19080 63008 -9864 -8148 2.31 2.15 6.18 196.43 Deviation (%)
Unit Operations Reactor Quenching Tower Flash separator
R-03 Q-01 F-01 Q-01 V07 V-08
1.46 8.02 27.16 1.99 15.29 9.01 0.29 12.38 13.61 4.90 8.24 6.47 1.02 17.13 16.13 18.62 4.78 0.24 6.42 17.20
Distillation Column
V-09 V-10
QR QC QR QC QR QC QR QC QR QC QR QC
V-11 Decanter Centrifugal Pump D-01 P-19 P-20 P-22 P-24
6.2.4 Discussion on Deviation By comparing the hand calculated data to the ASPEN data, it shows some deviations. However, the deviations are less than the 20% overall, so the deviations are still considered in the acceptable range. There are several reasons for deviation. Firstly, the deviation may due to the Aspen Property, UNIQ-RK chosen. In fact, several aspen property like NRTL, PENGROBINSON, PB-MODIFIED and etc were tried, UNIQ-RK present the best and reasonable result among them. UNIQ-RK is applicable for systems at low to moderate pressures (maximum pressure 10 atm) for which the vapour phase non-ideality is small. Hence, for unit operation whose pressure near to 10 atm or exceed it, UNIQ-RK does not suit the system, such as distillation column V-11, deviation is ~17% which is in the verge of acceptable range (Reboiler
55
Pressure of V-11=8atm). Such deviation may also due to the limitation of the ASPEN software where the separation of the component is unable to be achieved as in theoretically. Apart from that, when specific enthalpy, is being found, another assumption is made. The available equation for is: = +
2 1
() -----------------------------------------------------------------------------(6)
This equation can be applied for gas, liquid and solid phase. The part is neglected if the gas is an ideal gas or there is no pressure change for the solid and liquid. However, during the calculation, this part is neglected because we assumed that the pressure effect to the is very small if compared to the temperature effect part,
2 1
6.3 REFERENCES [1] Richard M.Felder, R.W.R., Elementary Principles of Chemical Processes. 2005, United States of America: Wiley International. [2] V.M.Gonzalez-Romero, N.C. Isothermal and Temperature and Temperature Programmed Kinetic Studies of Thermoset. Polymer Engineering and Science, 1989. 29(5). [3] Don W. Green, R.H.P., Perry Chemical Engineer's Handbook, D.W. Green, Editor. 2008, McGraw Hill.
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CHAPTER 7 PLANT LOCATION

7.1 SITE SELECTION CRITERIA FOR SITE SELECTION There can be plenty of criteria for choosing a competitiveness and attractiveness plant location. Among the general criteria that need to be considered before deciding for plant location are listed as 6 assessment, they are: 1) Site Strategy and positioning Availability of transportation, sea depth and land price. 2) Infrastructures and Facilities Facilities of Port, availability of utilities (power and water), availability of land area. 3) Malaysian Industrial Development Authoritys Approval (MIDA) 4) Relative Distance from Sourcing Market Basra light crude oil from Iraq (Middle East). 5) Relative Distance from Targeted Market Malaysia, China, India and Indonesia. 6) Economic and Administrative Environment By using the 6 significant criterion, four potential site location for instance, Pengerang, Johor; Pasir Gudang, Johor; Gebeng, Pahang and Kerteh, Terengganu are chosen to be compared. Table 7.1 is the tabulated result has been found mainly via the recent online news and sources. Table 7.1 Spider-web criteria comparison between potential site locations. Criterion Main Locations Factors Pengerang, Johor Pasir Gudang Gebeng, Pahang Kerteh, Terengganu (Tanjung Langsat, Johor) 1) Proximity to 1) Located 8 km from 1) 5 km from Kuantan 1) Kemaman Port 18m. 1. Site Location [1] [6] deepwater port Johor Port. Port [5] Strategy &Availab facilities. (eg. Johor 2) It is now an 2) Gebeng Industrial 2) Kertih Portand ility for Port, Pasir Gudang, established industrial Estate houses a centralised tankage Positionin Transpor Port of Tanjung area. [3] world-class facility. [6] g tation Pelepas, Jurong Port 3) Located 60 km from chemical and 3) Kuantan Port57
Sea Depth
and Keppel Port) [1] 2) Close to the international shipping route. (The Strait of Malacca/ South China Sea and Jurong island, [2] Singapore) 3) Proximity to the North-South Highway. 4) Close proximity with PETRONAS RAPID. [1] Natural water depths > 15m. [7] Pengerang deepwater terminal project will construct a deepwater jelly facility with water depth of 24 m. [8]
Tanjung Pelepas Port, a world-class container port. [3] 50 km from the Senai International Airport.
[4]
petrochemical industrial zone. [5] 3) East Coast Highway. (Links Kuala Lumpur and Kuantan)[3]
4) Tanjung Port is adjacent to acres of land in Langsat. [3]
Langsat located the 4000 industrial Tanjung
Centralised tankage facilities, container and bulk liquid port, railway linking Kertih, Gebeng and Kuantan Port. [3] 4) Centralised utility facilities, such as power, industrial gases, water and stream.[3]
Tanjung Langsat Port. Is equipped with a twinberth jetty consisting of outer (11 metres) and inner (6.5 metres) berths.
[3]
11.2-16.5m. [9]
21.6-22.9m. [10]
Land price 2. Infrastru ctures and Facilities Facilities
Land price: RM8-RM22 per square feet. [11] Pengerang deepwater terminal project, which is expected to be completed setup in the year 2017 to transform Pengerang into Asias Rotterdam Port. [8]
Land Price: RM8-RM22, per square feet. [11] 1) Johor Port has a 1000m berth and a hazardous cargo jetty [1] , Johor Ports Container Terminal
[12]. [1]
Land price: RM3RM11 per square feet.

[11]
Land price: RM0.18RM5.60 per square feet.

[11]
2) Tanjung
Langsat
1) Kuantan Port: Centralised tankage facilities which offers more than 3.4 km of berth for wide variety cargo ship. [3]
1) Centralised utility facilities.[13] 2) Centralised tankage terminal.[13] 3) Common warehouse.

[13]
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Water depth of 24 m would facilitate handling Very Large Crude Carriers (VLCC) and Ultra Large Crude Carriers (ULCC) [8]
Port. Is equipped with a twin-berth jetty consisting of outer (11 metres) and inner (6.5 metres) berths. [3]
2) Railway links Kerteh, Gebeng and Kuantan Port. [3] 3) 9km [5] pipeline and piperack system connecting Gebeng to Kuantan Port. [3] Main supplier Nasional (TNB). electricity is Tenaga Berhad Main electricity supplier is Tenaga Nasional Berhad (TNB).
Availabili ty of utilities (e.g. power, water)
Main electricity supplier is Tenaga Nasional Berhad (TNB).
Main electricity supplier is Tenaga Nasional Berhad (TNB).
Availabili ty of Land Area 3. MIDAs Approval*
Syarikat Air Johor Holding Bhd (SAJH) supply of the treated water. Raw water is sourced from sungai Layang, Sungai Johor and Sungai Pulai.[4] 22500 acres. [16]
Syarikat Air Johor Holding Bhd (SAJH) supply of the treated water. Raw water is sourced from sungai Layang, Sungai Johor and Sungai Pulai.[4] 183.70 acres land available. [4]
Water supply is from Seammbu Water [14] Treatment Plant.
Water falls under the jurisdiction of the state and is treated and distributed by the Terengganu Water Company (SATU).[15] 100 acres. [17]
1528.5 hectares (3776.99 acres) land available. [14] No opposition MIDA. from
Since it is PETRONAS private land, MIDA does not have much to say. Basra Light Crude Oil from Iraq (Middle East) Distance sailed (by
MIDA does not prefer the RAPID project.
MIDA is not 100% against the idea RAPID project. Basra Light Crude Oil from Iraq (Middle East) Distance sailed (by
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4. Relative Distance from Sourcing Market
Basra Light Crude Oil from Iraq (Middle East) Distance sailed (by
Basra Light Crude Oil from Iraq (Middle East) Distance sailed (by
shipping): From Basrah port to Pengerang Port is approximated 4380 miles. 5. Relative Distance from Targeted Market -Malaysia, China, India and Indonesia Distance from Pengerang Port to: 1) Xiamen(China)=180 0miles. 2) Chennai (India)=1825miles 3) Sibolga (Indonesia)=1065mil es Total 4690miles 6. Economic and Administ rative Environm ent -Political stability -Financial stability Governm ent Approval Procedure -Taxes Investmen t distance=
shipping): From Basrah port to Pasir Gudang Port = 4370 miles.[18]
shipping): From Basrah port to Kuantan Port = 4590 miles.[18]
shipping): From Basrah port to Kerteh Port = 4631 miles.[18]
-Malaysia, China, India and Indonesia Distance from Pasir Gudang to: 1) Xiamen(China)=188 8 miles. 2) Chennai (India)=1814miles 3) Sibolga (Indonesia)=1058mil es Total 4760miles distance=
-Malaysia, China, India and Indonesia Distance from Kuantan to: 1) Xiamen(China)=17 35 miles. 2) Chennai (India)=2035miles 3) Sibolga (Indonesia)=1280m iles
-Malaysia, China, India and Indonesia Distance from Kerteh to: 1) Xiamen(China)=170 3 miles. 2) Chennai (India)=2075miles 3) Sibolga (Indonesia)=1319mil es
1) RAPID is set to occupy over 6424 acres of PIPCs (Pengerang Integrated Petroleum Complex) 22500 acres. PIPC is a massive RM170 billion project that is expected to turn Malaysia into a mega petrochemical hub. [19]
1) More than 300 factories have provided more than 30,000 employment opportunities to the community of 100,000 people in Pasir Gudang. [4]
Total distance= 5050miles 1) The industrial estate is part of the Eastern Industrial Corridor which is the government backed economic region, envisioned by the Federal Government of Malaysia. 2) It is developed into an ultra-modern industrial region
Total 5097miles
distance=
1) Petrochemical and Industrial Park Development projects in Kertih Integrated Complex (KIPC) and Kertih Polymer Park.[21]
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servicing the 2) Federal petrochemical and Government chemical agencyJohor manufacturing Petroleum industries.[20] Development Corporation (JPDC) was created mainly as coordinator of PIPC [7] development. *Information obtained from design site location speaker, Mr. Yee Nai Tuck, Senior Deputy Director of Chemical Industry Division.
incentives
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Spider-Web (Site Selection Criteria for Several Locations) Pengerang

Site Strategy & Positioning 4 Economic & Administrative environment Pasir Gudang Gebeng Kerteh Infrasructure & Facilities
Table 7.2: Ranking of the criteria fulfillment for Pengerang, Pasir Gudang, Gebeng and Kerteh. ** Location Criteria Site Strategy & Positioning Infrasructure & Facilities MIDAs Approval Sourcing Market Targeted Market Economic & Administrative environment Pengerang 4 4 3 3 4 Pasir Gudang 3 3 4 4 3 Gebeng 1 2 3 2 2 Kerteh 2 1 1 1 1
3
2 1 0
Targeted Market
MIDAs Approval
Sourcing Market
Figure 7.1: Spider-web of the sites selection for RAPID project.
** Ranking marks are given based on the information that have been found and ranked by group members with consent.
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7.2 DECISION MAKING (PENGERANG, JOHOR) Among the comparison between four potential site locations, for instance Pengerang and Pasir Gudang in Johor; Gebeng in Pahang and Kerteh in Terengganu. Based on the radar chart as shown in figure 1, the blue region has covered the biggest portions, which mean Pengerang, Johor is a suitable and best choice for the RAPID plant development. Other than Pengerang, Pasir Gudang was ranked as second place, followed by Gebeng and Kerteh. The spider-web criteria to be compared are site strategy, infrastructure and facilities, MIDAs approval, sourcing and targeted market and last but not least, economics. Pengerang is chosen rather than Gebeng and Kerteh because one of the RAPID project targeted market is Indonesia while the sailing distance between Kuantan Port-Sibolga Port (1280 miles) and Kerteh Port- Sibolga Port (1319 miles) are farer than the sailing distance between Pngerang Port-Sibolga Port (1065 miles). By choosing Pengerang as the RAPID plant location, the shipping cost for exportation of the products to the Indonesia can be lowered due to the shorter distance of sailing. Thus, the Indonesia market can be secured by Pengerang rather than Gebeng and Kerteh. As a conclusion, Pengerang is the final decision as it is the most strategic location in accessibility to the targeted markets like China, India and Indonesia. Another main criterion to be looking into and make comparison between the four potential plant locations is the sea depth. Table 2 below is the deadweight tonnage of the tanker and its required sea depth. Table 7.3: Deadweight tonnage of the tanker with repect to the required sea depth. Tanker, DWT (tonnes) 10,000-50,000 50,000-80,000 80,000-120,000 120,000-200,000 Average Sea Depth required (m) 9.14 12.19 13.72 16.76
As the Pengerang has 24 m of sea depth compared to 6.5m-11m sea depth of Pasir Gudang Port, 11.2-16.5m in Gebeng Port and 21.6-22.9m in Kerteh Port. Pengerang has the advantageous of capable in carrying 120,000-200,000 DWT tankers. The larger amount of
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raw material can be imported from Middle East and inventory exported to China, India and Indonesia will result in high profit. Therefore, Pengerang is being chosen. In addition, Singapore is the major competitor for this RAPID project. However, Malaysia can easily get the lower-pay labour from Indonesia and Philipines than Singapore due to the high living cost in Singapore. Moreover, in terms of transport costs of crude oil from the Middle East and its geographic advantage of export distance to China and India, Malaysia has become increasingly competitive against Singapore. 7.3 OUTSTANDING CRITERIA OF PENGERANG Pengerang is chosen based on its strategic location, convenient accessibility, proximity sourcing and customer market, availability of infrastructures, investment cost level, economic growth and government support as below: 1) Strategic Location The Straits of Johor is one of the busiest international shipping routes in the world today. [22] Proximity to deepwater port, Johor Port, Pasir Gudang Port, Port of Tanjung Pelepas, Jurong Port and Keppel Port. 2) Accessibilities Located about 120 km from Johor Bahru.[22] Newly launched Senai- Desaru Expressway (Shorten travelling time by hours) [22] Pengerang Highway. [22] 116 km from Senai International Airport. [22] 147 km to Changi International Airport. [22] 407 km from KLIA. [22]
Figure 7. 2: Diagram shows the existing and proposed expressway in Johor. [22]
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3) Sourcing and Targeted Market The raw material is the crude oil from Basrah, Iraq. (Middle East). [23] From Basrah port to Pengerang is about 4380 miles. On the other hands, the crude oil can be imported from Russia, Myanmar and South American if the Basrah oil is in shortage. Finally, the petrochemical products of this project will be exported to China, India and for Malaysia demands. Distance from Pengerang to Xiamen (China) is about 1911 miles, to Chennai (India) is about 1789miles and to Sibolga (Indonesia) is about 1065miles.
[18]
Xiamen Port, China
Chennai Port, India
Basra oil from Middle East
Pengerang
Sibolga Port, Indonesia Export to China, India, Indonesia (Refined/ Petrochemical Products) Import from Iraq, Middle East (Crude oil)
Figure 7.3: Routes for the import of crude oil and export of petrochemical products. [Google image]
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4) Availability of Infrastructure (electricity and water) and Facilities Land price: RM8-RM22 per square feet in Pengerang, Pengerang, Johor. [11] Water depth of 24 m would facilitate handling Very Large Crude Carriers (VLCC) and Ultra Large Crude Carriers (ULCC) [8] Pengerang deepwater terminal project[8] and Johor Ports Bulk & Breakbulk Terminal [24] Facilities: Dedicated conveyor system, supported by rail-mounted quay cranes. Linear berthing length stretches to 2.4km with draught up to 13.5m. Ample storage facility of over 230,000sqm for bulk & break bulk cargo. Efficient logistics solutions for all cargo needs. Experienced and skilled stevedores of various grades in handling cargo and working aboard vessels. Syarikat Air Johor Holding Bhd (SAJH) supply of the treated water. Raw water is sourced from sungai Layang, Sungai Johor and Sungai Pulai. [4] Main electricity supplier is Tenaga Nasional Berhad (TNB).
5) Economic Growth and Government Support RAPID is set to occupy over 6424 acres of PIPCs (Pengerang Integrated Petroleum Complex) 22500 acres. PIPC is a massive RM170 billion project that is expected to turn Malaysia into a mega petrochemical hub. [19] A new dedicated Federal Government agency- Johor Petroleum Development Corporation (JPDC) was created mainly as coordinator of PIPC development as well as one-stop information centre to assist investors, oil and gas players and local community. [7] Malaysian Industrial Development Authority (MIDA)s approval.
6) Investment Cost level About RM120 bil worth of investments have been earmarked by Petronas including RM60 bil by the national oil and up to RM38 bil by KuoKuang Petrochemical Technology Co., a Taiwanese company. [25]
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7.4 REFERENCES [1] Pengerang Petroleum & Maritime Industrial Park. Retrieved 18 November 2012, from http://www.pengerangmaritime.com.my/benefits.html [2] Pengerang Petroleum & Maritime Industrial Park. Retrieved 17 November 2012, from http://www.pengerangmaritime.com.my/development.html [3] Profit from Malaysias Petrochemical Industry. Retrieved 18 November 2012, from http://www.pengerangmaritime.com.my/img/Petrochemical_Incentives_by_MIDA.pdf [4] Iskandar Malaysia. (2008) Important Facts and Details on Eastern Gate Development. Retrieved 12 October 2012, from http://www.iskandarmalaysia.com.my/pdf/brochures/Flagship-D-EN.pdf [5] The official portal invest in Pahang. Gebeng Industrial Estate. Retrieved 24 November 2012, from http://www.investinpahang.gov.my/index.php?ch=en_investinpahang&pg=en_industriala reas&ac=9 [6] Dialog Group. Retrieved 18 November 2012, from http://www.google.com.my/url?sa=t&rct=j&q=&esrc=s&source=web&cd=6&cad=rja&v ed=0CEAQFjAF&url=http%3A%2F%2Fwww.bpam.com.my%2Finc%2FfileDownload_ 1.asp%3Ffile_loc%3D%2Fothers%2Fresearch%2F%26file_name%3D%255B53084%25 5D20120427%2520DIALOG%2520GROUP.pdf%26Size%3D&ei=dqGoUMfzAcLorQe 1tIGYAw&usg=AFQjCNFTGh3wTh49I37dWBws8_5ssJ_Eqg [7] Malaysia Petroleum Resources Corporation (MPRC). Retrieved 18 November 2012, from http://www.mprc.gov.my/index.php/invest/pipc [8] Dialog Group berhad. About Pengerang Deepwater Terminal. Retrieved on 17 November 2012, from http://www.dialogasia.com/i_annual/DIALOG2012-Main.pdf [9]The Port. Facilities. Berth. Retrieved 2 December 2012, from http://www.ijm.com/infrastructure/port/KuantanPort/thePort/fac_berth.asp?hidReLocatio nMenu=1 [10]Port of Kertih, Malaysia. Retrieved 25 November 2012, from http://ports.com/malaysia/port-of-kertih/ [11]MIDA Official Website. Retrieved 25 November 2012, from http://www.mida.gov.my/env3/index.php?page=cost-of-industrial-land-factory-building [12]Johor Port Container Terminal. Retrieved 20 November 2012, from http://www.johorport.com.my/facilities/container-terminal [13]Kertih Port. Retrieved 25 November 2012, from http://www.ecerdc.com.my/ecerdc/oil2.htm [14]Kuantan Port Facilities. Retrieved 24 November 2012, from http://www.investinpahang.gov.my/index.php?rp=kuantan_port_a3.pdf [15]Minding the bottomline. Retrieved 24 November 2012, from http://www.terengganu.gov.my/maxc2020/appshare/widget/mn_img/1/CP8%20HAVEN%20'07%20CO.pdf [16] Behind the Pengerang land grab. Retrieved 25 November 2012, from http://malaysiachronicle.com/index.php?option=com_k2&view=item&id=42029:pengerang-land-grabsgor-pr-govt-said-no-but-greedy-johor-bn-said-yes&Itemid=2
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[17]Kerteh, Terengganu. Retrieved 25 November 2012, from http://www.iproperty.com.my/propertylisting/486107/Kerteh_Industrial_Land_ForSale [18]Portworld. Consumption calculation. Retrieved 24 November 2012, from http://www.portworld.com/map/ [19] The Malaysian Insider. Protest begins against Petronas RM60b Pengerang project. Retrieved on 18 November 2012, from http://www.themalaysianinsider.com/litee/malaysia/article/protest-begins-againstpetronas-rm60b-pengerang-project [20]Gebeng Industrial Estate. Retrieved 25 November 2012, from http://wikimapia.org/1568627/Gebeng-Industrial-Estate [21]East coast economic region. Retrieved 25 November 2012, from http://www.mia.org.my/new/downloads/circularsandresources/budget/2012/section_b/ b23.pdf [22]Pengerang Petroleum & Maritime Industrial Park. Retrieved 25 November 2012, from http://www.pengerangmaritime.com.my/location.html [23]Basra Light Crude Oil. Retrieved 25 November 2012, from http://www.bp.com/extendedsectiongenericarticle.do?categoryId=9035920&contentId =70665 [24]Bulk & Breakbulk Terminal. Retrieved 19 November 2012, from http://www.johorport.com.my/facilities/bulk-breakbulk-terminal [25]Thestar online. Rotterdam of the East. Retrieved 18 November 2012, from http://biz.thestar.com.my/news/story.asp?file=/2012/6/9/business/11445098&sec=busi ness
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CHAPTER 8: ECONOMY FEASIBILITY STUDY

8.1 LAND COST ESTIMATION The purpose site location of this acrylonitrile plant is in Pengerang Johor. It would require large amounts of land for refinery, hydro-treating, FCC and petrochemical plants. Hence, the land cost estimation is calculated based on the existing plant by using proportional relation as shown in Appendix B. The land price at the proposed location is approximately RM 20/ft2[1]. The total land area estimated for this proposed acrylonitrile plant is 860.48 acres which valued USD 249,883,392.30 equates to RM 749,650,176.80. 8.1.1 Refinery and Hydro-treating Plant For refinery and hydro-treating plant, the land cost estimation is based on the existing crude oil refinery plant from PETRONAS Group. The land area for the refinery plant which produces 265,000 barrels/day is estimated to be 926 acres[2]. As our refinery plant is designed processes 150,000 barrels/day of crude oil. By using proportional relation to related the land area to the total refinery plant, 926 acres land needed For a 265,000 barrels/day processing plant X land needed For a 150,000 ton ethylene/year production plant X = 524.15 acres = 2.12 x 106 m2 = 22,831,974 ft 2 The estimation of land price for refinery and hydro-treating plant, = 22,831,974 ft 2 x RM 20/ ft2 = RM 456,639,480 = USD 152,213,160
8.1.2 Fluid Catalytic Cracking Plant (FCC) The land cost estimation is based on the existing naphtha cracking plant from MTBE (M) Sdn Bhd. MTBE (M) Sdn Bhd has a annual propylene production of 380,000 ton of propylene/year production plant [3]. According to the Official Website Kuantan Port Authority, the land area for the cracker plant is 23.62 acres[4]. Propylene production in FCC plant is 178,584 ton of propylene/year production plant.
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By using proportional relation estimation, 23.62 acres 380,000 ton of propylene/ year production plant X acre 178,584 ton of propylene/ year production plant X = 11.1 acres = 44920.11 m2 = 483516.04 ft2 The estimation of land price for fluid catalytic cracking, = 483516.04 ft2 x RM 20/ ft2 = RM 9,670,320.80 = USD 3,223,440.27
8.1.3 Petrochemical Plant The land cost estimation is based on the existing Acrylonitrile plant from Grand Pacific Petrochemical Corp[5]. As there is no single acrylonitrile plant in Malaysia can produce high production rate of acrylonitrile, hence foreign countrys acrylonitrile plant is taken as reference in estimating the plant size. The land area for the acrylonitrile plant which produces 100,000 ton acrylonitrile/year is estimated to be 32 acres[6].
By using proportional relation to related the land area to the total production of acrylonitrile, 32 acres land needed For a 100,000 ton acrylonitrile /year production plant X land needed For a 120,000 ton acrylonitrile/year production plant X = 38.4 acres = 1.55 x105 m2 = 1672704 ft 2 The estimation of land price for fluid catalytic cracking, = 1672704 ft 2 x RM 20/ ft2 = RM 33,454,080 = USD 11,151,360
Future changes may make it desirable or necessary to expand the plant facilities, thus an additional of 50% from the land area required is taken for the future expansion, = 0.5 x 573.65 acres = 286.83 acres = 1160759.83 m2 = 12,494,314.80 ft2 = 12,494,314.80 ft2 x RM 20/ ft2 = RM 249,886,296 = USD 83,295,432
Hence the total land area required including the land needed for future expansion purpose is 860.48 acres. The total land price required for this acrylonitrile plant,
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Total land price = USD 152,213,160.00 + USD 3,223,440.27 + USD 11,151,360 + USD 83,295,432 = USD 249,883,392.30 = RM 749,650,176.80
8.2 TOTAL CAPITAL INVESTMENT Before a new plant can be put into operation, there is capital to purchase and install the required machinery and equipments. The capital needed to supply the required manufacturing and plant facilities is fixed capital investment (FCI), whereas the necessary for the operation of the plant is working capital investment (WCI). The sum of these two necessary capitals is known as the total capital investment (TCI). 8.2.1 Fixed Capital Investment Estimation of FCI is calculated using cost index where if the cost at some time in the past is known, the equivalent cost at present can be determined by multiplying the original cost by the ratio of the present index value to the index value applicable when the original cost was obtained as shown by the equation below,
index value at present index va lue at time original cost was obtained
Present cost = original cost
---------(1)
The Marshall and Swift equipment indexes are used as the cost index conversion to current year. The value of the cost indexes are based on Table 8.1 and a straight line is extrapolated to predict the Marshall and Swift installed-equipment index[7] in the year 2007 and 2012. The index in the year 2007 is taken as the base year since the price of the equipment is referred to that year[8]. Table 8.1 : Marshall and Swift installed-equipment indexes for process industry. [7] Year 1987 1988 1989 1990 1991 1992 1993 Marshall and Swift installed-equipment Indexes 830.0 859.3 905.6 929.3 949.9 957.9 971.4
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1994 992.8 1995 1029.0 1996 1048.5 1997 1063.7 1998 1077.1 1999 1081.9 2000 1097.7 2001 1106.9 2002 1116.9 The estimated cost index value is obtained from the graph as shown in Figure 8.1. The estimated cost index value is 1496.403 in the year 2007 and 1654.548 in the year 2012.
Marshall and Swift installedequipment Indexes
2000 1800 1600 1400 1200 1000 800 600 400 200 0
Graph of Marshall and Swift installed-equipment Indexes versus year

y = 31.629x - 61983 R = 0.9384
Year
1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020
Figure 8.1: Extrapolation graph of Marshall and Swift installed-equipment index versus year. Each individual piece of equipment on the Process Flow Diagram was priced according to procedures outlined in Plant Design and Economics for Chemical Engineering handbook. The overall equipment cost determined is summarized in Table 8.2. The price of each piece of equipment is calculated as below using equation (1). For Storage Tank, Price in Year 2012 = USD 75,000.00 1654.548 1496.403 = USD 82,926.26
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Table 8.2: Estimation of Cost of Purchased-Equipment. Unit Operation Quantity Price per unit 2007 (USD) 75,000.00 200,000.00 70,000.00 50,000.00 10,000 500,000.00 200,000.00 20,000.00 20,000.00 20,000.00 21,400.00 30,900.00 40,000.00 400,000.00 60,000.00 40,000.00 78,000.00 56,000.00 10,000.00 8,000.00 Price per unit 2012 (USD) 82,926.26 221,136.69 77,397.84 55,284.17 11,056.83 552,841.71 221,136.69 22,113.67 22,113.67 22,113.67 23,661.63 34,165.62 44,227.34 442,273.37 66,341.01 44,227.34 86,243.31 61,918.27 11,056.83 8,845.47 Total (USD) 663,410.06 221,136.69 Cost
Storage tank 8 Atmospheric Distillation Unit 1 Reactor Heat exchanger Pump Distillation Column 4 10 25 12 2 1 1 1 2 1 1 1 2 2 1 2 2 2
309,591.36 552,841.71 276,420.86 6,634,100.57 Heater 442,273.37 Furnace 22,113.67 Desalter 22,113.67 Quenching tower 22,113.67 Adsorber 47,323.25 Flash separator 34,165.62 Decanter 44,227.34 Gas Membrane 442,273.37 Mixer 132,682.01 Condenser 88,454.67 Boiler 86,243.31 Cooler 123,836.54 Accumulator 22,113.67 Compressor 17,690.93 Total Purchased Equipment 10,205,126.34 [9] *Note: 1 USD= RM 3.00 . MYR is projected to appreciate against the USD and stabilize at an exchange rate of RM3.00 per USD for the coming 4years (2012-2015). The typical percentage of FCI values for fluid process plant from Table 8.3[7] showed the breakdown percentage range of each component for FCI. An optimum percentage value is selected from the range and tabled as shown in Table 8.3. Hence, FCI of proposed plant is estimated at USD 294,816,185.62 which equates to RM 884,448,556.80.
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Table 8.3: Breakdown of Estimated Cost of FCI. Component Direct Costs Purchased Equipment Installation and delivery Instrumentation and Controls Piping Electrical Systems Buildings Yard Improvements Service Facilities Land Total Direct Costs Indirect Costs Engineering and Supervision Construction Expenses Legal Expenses Contractors Fee Contigency Total Indirect Costs Percentage Range (%) 15-40 6-14 2-12 4-17 2-10 2-18 2-8 8-30 Pre-calculated Selected Range (%) Cost (USD)
27 12 6 13 6 10 4 10
10,205,126.34 4,898,460.64 2,449,230.32 5,306,665.70 2,449,230.32 4,082,050.54 1,632,820.21 4,082,050.54 249,883,392.30 284,989,026.92
4-20 4-17 1-3 2-6 5-15
8 7 2 2 7
3,023,741.14 2,645,773.50 755,935.28 755,935.28 2,645,773.50 9,827,158.70 294,816,185.62
Fixed Capital Investment= Total Direct Costs+ Total Indirect Cost 8.2.2 Working Capital Investment
Working capital investment is the amount of money required to expand the business, meet short-term business responsibilities and cover business expenses.[10] In easy words, it is the initial investment for the operation of plant at the moment it is operated. It includes raw materials and supplies carried in stock, finished products in stock and semi finished products in the process of being manufactured, accounts receivable, cash kept on hand for monthly payment of operating expenses, salaries, wages, raw-material purchases, accounts payable, and taxes payable. The ratio of working capital to total capital investment varies with different companies, but most chemical plants use 20 percent of the total capital investment. [11] From calculation below, WCI is estimated to be approximately USD 73,704,046.4.
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From the formula derived from definition[11], = 0.2 Where, = + = + 0.2 1 0.2 = = Then, 0.8
294,816 ,185 .62 0.8
= 368,520,232 And = 73,704,046.40
Thus, total capital investment is estimated USD 368,520,232 for the proposed acrylonitrile plant. 8.3 TOTAL PRODUCTION COST 8.3.1 Raw Material Cost (Anually) Table 8.4: Raw material cost calculation. Materials Part of plant Price (USD) Quantity needed Total (USD) Sour crude oil Refinery Per 87.52[12] Water All parts of plant Per m3 = 0.95[13] 197.544m3 1,588,253.60 4,399,468,254 barrel= 50,250,000 barrel 4,397,880,000 price
Total raw material cost
For the process, sour crude oil is treated as the feedstock to produce the product of acrylonitrile, and also the co-product of hydrogen cyanide and acetonitrile. The pricing of sour crude oil for 2012 is USD 87.52 per barrel[12]. 150,000 barrel of sour crude oil per day is
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used in the process, which means 50,250,000 barrel is used annually. Thus, the sour crude oil cost is estimated about USD 4,397,880,000. While for the water supply which is obtained from Syarikat Air Johor Holding Bhd (SAJH), the price for industry water is USD 0.95/m3[13]. The total water flow rate for the whole plant to produce 100,000 tons of acrylonitrile per year which is obtained from the mass balance is 175040 kg/hr (for overall plant) + 17504 kg/hr (for miscellaneous purpose) + 500kg/hr (for FCC plant). Thus, the overall water consumption is 1,548,053.76 tons/year. Thus, water supply cost is estimated USD 1,558,253.60. The overall raw material cost is USD 4,399,468,254. 8.3.2 Catalyst Cost Table 8.5: Catalyst cost calculation. Catalyst Part of Plant Price (USD) Per 25g = 93[14] Quantity needed Total (USD) BismuthMolybdenum Oxide NickelMolybdenum SAPO-11 Catalyst MFI Zeolite Fluid Catalytic Per 100g=200[16] 89,592 kg 179,184,000 Hydro-treating Per 1 kg = 26[15] 14,816 kg 385,216 Petrochemical 100 kg 372,000 Price
Cracking Fluid Catalytic Per =316.62

[17]
500g 890 kg
563,583.60
Cracking Total Catalyst Cost
180,504,799.6
Catalyst used in the refinery section is Bismuth-Molybdenum Oxide. The market price for the catalyst is USD93 per 25g[14], and 100kg is needed. Thus, the cost is USD 372,000. In the hydro-treating plant section, Nickel-Molybdenum is being chosen as the catalyst. As 14,816 kg is needed, the cost will be USD 385,216.
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While for FCC, SAPO-11 catalyst and MFI Zeolite are needed, this accounts for USD 179,184,000 and USD 563,583.60 respectively. From overall calculation, the total cost is USD 180,504,799.60. However, as the catalyst is only renewed after 3 years, thus the value of the total catalyst cost is being divided by 3 (average for annual cost). Thus, the annual cost for catalyst is USD 60,168,266.53. 8.3.3 Total Production Cost Total product cost (TPC) estimation covers the annual cost for operating plant, and this includes the manufacturing cost and also general expenses. To calculate the subdivision of these costs, an optimum percentage value is selected from the typical percentage of TPC values recommended for a fluid process plant. [11] By using the method, the component cost are calculated and tabled as below. The estimated Total Product Cost (TPC) is USD 7,332,447,090. Table 8.6: Breakdown of Estimated Cost TPC. Components Percentage Range Selected Percentage MANUFACTURING COST 1) Direct Production costs a) Raw materials b) Operating labor c) Operating supervision 10-60% of TPC 10-20% of TPC 15% of cost 60% of TPC 10% of TPC 4,399,468,254 733,244,709 Estimated (USD) cost
for 15% of cost for 109,986,706.40 operating labor 5% of TPC 659,920,238.10
operating labor d)Utilities electricity) e) Maintenance and repairs f) Operating supplies 2-10% of FCI 15% of cost (steam, 5-20% of TPC
5% of FCI
14,740,809.28
for 15% of cost for 1,586,405.65 and maintenance repairs and
maintenance repairs g) Laboratory charges
10-20% of cost for 10% of cost for 73,324,470.90 operating labors operating labors 2% of TPC 146,648,941.8
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h) Patent and royalties
0-6% of TPC
i) Catalyst and Solvent 2) Fixed charges a) Depreciation b) Taxes (property) c) Financing 3) Plant Overhead Cost a)Medical, Safety
Based on usage
Pre-calculated
60,168,266.53
10% of FCI 1-2% of FCI 10% of TCI
10% of FCI 1% of FCI 10% of TCI
29,481,618.56 2,948,161.86 36,852,023.2
and 50-70% of total for 50% of total for 440,818,482 labor, operating operating and supervision, maintenance and labor,
protection, Storage facilities, operating General plant overhead, etc operating supervision, maintenance
Total Manufacturing cost = USD6,709,189,087.30 GENERAL EXPENSES a) Administrative 15-25% of operating 15% of cost for 109,986,706.40 labor b)Distribution Marketing expenses c) Research and 5% of TPC 5% of TPC 366,622,354.50 and 2-20% of TPC operating labor 2% of TPC 146,648,941.80
Development Total General Expenses cost = USD 623,258,002.70 Total Product Cost (TPC) = Total Manufacturing costs + Total General Expenses = USD7,332,447,090
* TPC= Total Product Cost FCI=Fixed Capital Investment TCI=Total Capital Investment
8.4 PROFITABILITY ANALYSIS 8.4.1 Gross Profit In the planning, the proposed acrylonitrile plant will be shut down for maintenance for 30 days per year. While for the operating time, the plant is scheduled to be working for 24 hours, to produce the product of acrylonitrile, and also the co-product of hydrogen cyanide,
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and acetonitrile. The table below showed that the grsss profit of proposed acrylonitrile plant per year is USD 205,717,879.80. Table 8.7: Gross profit calculation. Products Unit price of selling Production capacity Total profit (USD/ton) (ton/year) (USD/year) USD1779[18] 120,000 213,480,000 Acrylonitrile USD1145.10[19] 8265.12 9,464,388.91 Hydrogen Cyanide USD2124.80[20] 3055.2 6,491,688.96 Acetonitrile USD929[21] 892,400 829,039,600 Heavy Naphtha USD1002.89[22] 1,707,696 1,712,631,241 Kerosene 2,341,248 3,305,842,176 AGO (Automobile oil) USD1412[23] USD1005.50[24] 1,449,129.6 1,457,099,813 Diesel USD880[18] 3,470 3,053,600 Ethylene USD26[25] 37,788 1,095,852 Carbon dioxide 7,538,164,970 Annual profit 7,332,447,090 Total product cost (TPC) 205,717,879.80 Gross profit (before taxation) *Refer to Chapter 10 Appendix, sample calculation for gross profit is performed. 8.4.2 Taxation Policy in Malaysia As a manufacturing plant, MIDA (Malaysia Industrial Development Authority) will give incentives in the form of 5 years partial exemption from the payment of income tax. On top of that, other incentives include[26]: 1) Investment Tax Allowance up to 60% of allowance on qualifying capital expenditure (factory, plant, machinery or other equipment used for the approved project) within five years from the date of first qualifying capital expenditure. 2) Exemption from Import Duty on Raw Materials/Components - regardless of whether the finished products are for export or domestic market. 3) Exemption from Import Duty and Sales Tax on Machinery and Equipment- on machinery/equipment used in manufacturing process which are not produced locally.
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Table 8.8: Total net profit calculation after taxation. Plant operating period Yearly Net Profit (After Total Net Profit, USD (times with 5 years for each operating period) 1st to 5th year 5th to 10th year 182,266,041.50 127,545,085.50 911,330,207.50 637,725,427.40 1,549,055.635 930,652,010.7
Taxation), USD
Total Net Profit for 10 years Plant Operation Total Net Profit minus the payback cost
*Refer to Chapter 10 Appendix, sample calculation is performed. In the initial 5 years of operation, only 30% of annual plants gross profit is subjected to a tax of 38%, which complies with the Petroleum Income Tax. Then after 5 year ends, the normal tax rate of 38% of plants gross profit applies. [27] As the annual gross profit is estimated USD 205,717,879.80, the total annual net profit of the plant after taxation is being tabulated in table 8.8 above. The plant is expected to be working for at least 10 years, thus the total net profit earned by the plant (minus the payback period) is USD 930,652,010.7 by referring to the figure 8.2, which is the y-axis value of the net profit over total life of project. This indicates that investment on the acrylonitrile plant is feasible and profitable. 8.5 PAYBACK PERIOD To find the payback period, a cumulative cash flow diagram is plotted. The diagram depicts the economic feasibility of the proposed acrylonitrile plant, over an estimated lifetime period of 10 years after the commission. The ground breaking is scheduled to be done in 2013, and as the construction period is expected to be 3 years, the proposed plant will be commissioned in 2016. This is because, the proposed plant location has the required infrastructures/facilities for the plant, and thus lesser time is needed for the overall commissioning to be started. As we can see from the graph, the payback period in which it is time required for the return on an investment in order to repay the sum of the original investment, is 3.4 years.
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Figure 8.2: Graph of cumulative cash position for proposed new Acrylonitrile plant. *Refer to Chapter 10 Appendix, some description of the payback period graph is stated.
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8.6
REFERENCES
[1]MIDA. Cost of Industrial Land & Factory Building (2012 ). Retrieved 5 November 2012, from http://www.mida.gov.my/env3/index.php?page=cost-of-industrial-land-factorybuilding. [2]Petronas. Malacca Refinery Complex (2009). Retrieved 30 November 2012, from References www.petronas.com.my/media-relations/.../Nada_2009_2.pdf. [3]Technologies, J. Market data Malaysia. (2009). Retrieved 24 November 2012, from http://www.apic-online.org/countrydata_malaysia.htm. [4]Authority, K.P. Sub-Leasing of Land. (2002). Retrieved 24 November 2012, from http://www.lpktn.gov.my/v3r4e/index.php?option=com_content&&view=article&&id=2 4&&Itemid=9&&template=green_lpktn. [5]Management, I.A. (2012). Retrieved 30November 2012, from http://www.usedplants.com/plants-for-sale/77.html [6]Asia, B.D. ASIAN SPECIALTY CHEMICALS NEWSLETTER (2001). Retrieved 30 November 2012, from from: http://www.bdallc.com/wp-content/uploads/2012/08/242.pdf. [7]M. S. Peter, K.D.T., R. E. (2002). West, Plant Design and Economics for Chemical Engineering Vol. 5th. Mc Graw Hill. [8]Matches. Equipment Costs. (2007). Retrieved 30 November 2012, from http://matche.com/EquipCost/index.htm. [9]Malaysia, B.N. Ringgit Foreign Exchange Rates. (2012). Retrieved 2 November 2012, from http://www.bnm.gov.my/index.php?tpl=exchangerates. [10] UK, C.i., Capital Investment. 2012. [11] M. S. Peter, K.D.T., R. E. (2002). West Plant Design and Economics for Chemical Engineering (4th Ed). , Plant Design and Economics for Chemical Engineering (4th Ed). [12] World, R., World Crude Oil Price. 2012. [13] KeTTHA, Kadar Tarif Air di Malaysia. 2010. [14] Biotechnology, S.C., Bismuth-Molybdenum Oxide catalyst price. 2012. [15] Daily, S., Nickel-Molybdenum catalyst price. 2012. [16] Material, A., SAPO-11 catalyst price. 2012. [17] Sigma-Aldrich, MFI Zeolite Catalyst Price. 2012. [18] Fibre2fashion, Acrylonitrile Pricing. 2012. [19] ICheme, Chemical Cost Guide. 2008. [20] Alibaba, Acetonitrile pricing. 2012. [21] YNFX, Naphtha pricing. 2012. [22] theStar, Kerosene, diesel prices up in review. 2012. [23] Agency, I.E., Automobile oil Price. 2012. [24] Association, F.T., Weekly Fuel Prices. 2012. [25] Cozijnsen, J., CO2 price in 2012. 2012. [26] MIDA, Incentives for Investment. 2012. [27] MIDA, Invest in Malaysia : Taxation. 2012.
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CHAPTER 9 SAFETY, HEALTH AND ENVIRONMENT (SHE)

9.1 INTRODUCTION The question "How important is SHE management to RAPID?" Analyst Jill
Feblowitz of IDC Energy Insights, the number one prediction for the Oil & Gas Industry this year,2012 is new regulatory requirements will drive increased investment by oil and gas companies in Health, Safety, and Environment (HSE) system enhancements, upgrades, and replacements. Incident tracking and management, corrective action and regulatory reporting will be addressed first and will depend on application integration [1]. With his prediction is specific to the Oil & Gas industry, it can be realize that how importance SHE practices in oil and gas industry. The primary objective of Health, Safety, and Environment initiatives is to reduce overall risk, to comply with Federal, State and Local regulations, and to create a safe yet efficient operating environment for a management team.
9.2 SAFETY ASPECTS Safety is of extreme importance in all petroleum refineries. Every employee is involved in developing the regulations and procedures for work safety. In this way, anyone who works in the refinery is part of the safety system and will always be sure to work safely and help others work safely[6]. All routine jobs in the refinery should conform to high safety standards.
9.2.1 Personal Protective Equipment (PPE) All the workers will be supplied with Personal Protective Equipment (PPE) such as safety helmets, safety shoes, masks and safety goggles that are compulsory for them to wear while working in the plant area. If in any case the employees are failed to do so, a warning or appropriate actions will be t aken. To ensure that the PPEs are in a good condition, it will be inspected at least once every two months to make sure it is in a good quality.
9.2.2 Permit to Work For the workers that will handle the job which involves hot or cold material, they need to have a cold or hot work permit that will be issued by the management office. On top of that, there will also be a confined work space permit, for the workers that will enter the big equipments (distillation, reactor and separator) for cleaning, maintenance andplant shut-
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downpurpose. This is to ensure that the plant workers conducting the job is being supervised and permitted by the management.
9.2.3 Appropriate Labelling/ Hazard Rating/ Safety Data Sheet Labelling and hazard rating are important so that it will inform the workers about the risk that they take while performing the specific tasks. Warning, safety signs or safety instructions will be posted at each of the entrance at RAPID, so that it will be a constant reminder to the workers. As the plant workers might be from different backgrounds or ethnicity, the signs must at least be in four different languages such as English, Malay, Chinese, and Indian. On top of that, the piping should also be coloured according to the condition of the streams that flows through it. As an example, red pipe for the hot stream, green pipe for the cooling water stream. While for the equipments, the safety manual on how to operate it safely must be provided, and it also must be labelled according to the plant process flow diagram (PFD). These are essential to help the engineers and operators on site to trace and identify each specific piping streams and equipment especially during pipeline troubleshooting or modifications. Besides that, the safety data sheet must also be supplied to the workers who are dealing with the chemicals. Material safety data sheet (MSDS) is one of the examples that can help the workers to identify the hazards and take appropriate safety measures while handling the chemical.
9.2.4 Workplace Conditions The workplace must be ensured to have a proper lighting, noise insulator, some heat controlling system and also well-ventilated. While for the plant floor area, it should be clean, dry and non-slippery to avoid any accidents from happening. Besides that, the plant layout itself must be arranged systematically so that there will be adequate space for the workers to operate them safely.[2] The control room or office near the plant side should also be surrounded by sound proof material, in order to prevent the noise which comes from the plant to enter the area, in which many people in the plant might be working.
9.2.5 Maintenance/ Regular Inspection Plant maintenance is the methods, strategies, and practices to keep an industrial factory running efficiently.[3] The general aim is to create a productive working environment that is also safe for workers, and it includes regular check-up of equipment to make sure that
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they are functioning properly, and to repair it immediately if anything goes wrong. A maintenance plan will also be prepared, which include scheduling times for equipment checkups, trouble-shooting, and general clean-up.
9.2.6 Storage and Handling A specially designated area should be provided to keep raw materials and chemicals that are hazardous. No smoking, flames, heat or any sources of ignition should be allowed in chemical storerooms, and it must be well-ventilated. On top of that, the chemical containers should be tightly closed until it ready to use, in order to prevent any leakages, contamination and also to prevent the reaction with air (for reactive chemicals). The storerooms must also be free from floor drains, to prevent the contamination of water supply in case if any leakage occurs. Warning must also be issued at the entrance of the storeroom to inform the workers about the hazards.
9.2.7 Emergency Plant Safety System The emergency plant safety system is an additional safety features that should be installed, to serve as a backup in case if the preventive measures taken are insufficient. a)Gas Detector It is a device which detects the presence of various gases within an area, and is used to detect a gas leak and aligned itself with a control system so a process can be automatically shut down. Gas detector can also sound an alarm in case if leak is occurring, giving warning to the workers in plant area.[4] Gas detectors should be installed around the plant and inspection should be done from time to time to ensure the detectors are in good condition. b) Blast Wall It is a heavy wall that is used to isolate buildings or areas which contain highly combustible or explosive materials, and to protect the surrounding unit operation from blast damage when exposed to explosions due to high internal pressure. c) Control and Alarm System This involves the process control system, which is based on the efficient production and also to ensure the process safety. The level, pressure and temperature control systems must be installed to automate the overall production process. On top of that, the alarm system and interlock system needs to be installed to alert operators in case there are any deviations in the
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process conditions. The safety alarm can also be connected to the operating system, so that necessary safety measures can be taken to hold the system off. d) Fire-Fighting System The system consists of the sea inlet(s), suction piping, fire pumps and also a distributed piping system supplying fire hydrants, hoses and nozzles located throughout the vessel. It provides a readily available source of water, in which different level of fire hazards require different types of stream: Straight stream to combat a deep seated fires, or as sprays to combat combustible liquid fires where cooling and minimum agitation is desired. [5]
9.3 HAZARD ANALYSIS 9.3.1 Introduction Hazard analysis is a tool for systematically identifying and assessing the hazards and risks associated with a facility and, on the basis of agreed criteria, forming judgements about the acceptability of those risks to the surrounding locality. With hazard analysis, design and operation can be carried out with an adequate level of safety. A schematic of the hazard analysis process is included in figure 9.1 below.
Hazard Identification
Figure 9.1: Basic methodology for hazard analysis.
Analysis
Estimate Consequences
Estimate Likelihood
Calculate Risk
Compare Against Criteria
Assessment
Consider Risk Mitigation and Management Options
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9.3.2 Hazard Identification Hazard identification involves the systematic identification of possible hazards, both on-site and off-site. Hazard identification requires the consideration of all the relevant available information regarding the facility. This might typically include: Site and plant layout. Detailed process information in the form of engineering diagrams and operating conditions. The nature and quantities of materials being handled. Operational, organization and physical safeguard. There are a number of useful hazard identification techniques such as Hazard and Operability Study (HAZOP), Failure Modes and Effect Analysis (FMECA), Fault Tree Analysis (FTA) and Event Tree Analysis. Table 9.1 represents the general hazard identification for a RAPID plant. Table 9.1: Hazard identification for RAPID plant. No. Events 1 Petroleum tank fire Causes -Static electricity builds up and sparks due to fast filling. -Pressure vent valve fails, tank root fails and ignition. Possible Consequences -Tank roof may fail fire of entire roof area. If not controlled or extinguished may involve other tanks in same compound. Prevention -Pressure vent valves checked prior to fill/ or discharge. -Water cooling system set on each tank.
Petrochemical -Adjacent tank fire or bund fire tank fire heating tank contents to decomposition.
-Emission of toxic products or vapours. Downwind effect depends on toxicant released and wind/stability conditions.
-Tanks placed in separate bund. -Cooling system on all tanks.
Pipe failure
-Mechanical impact. -Corrosion. -Mechanical impact. -Corrosion. -Failure of tank
-Gas disperses. If -Area drained. ignited may result in -Gas detectors around flash fire. perimeter of LPG area. -On dispersion, vapour may form a gas cloud. -If ignited, may result -Isolation fitted with pressure relief valves, discharge vertical to atmosphere.
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Large leak
or associated in flash fire. fittings, pump or pipe work and ignition.
-Gas detection on perimeter of LPG area.
9.3.3 Hazards Analysis of Four Plants a)Petroleum Refineries, Hydro-Treating and FCC Units Table 9.2 below shows the hazard analysis conducted for the major processes taking place in refinery unit. Besides, precaution steps are suggested to minimize the hazards to bottom level. Table 9.2: Hazard analysis and precaution steps in refineries unit [1]. Process Potential Hazards Crude Oil Hydrogen sulphide, hydrogen chloride and salts in the desalter are the main causes of Precorrosion in the unit. Corrosion is the source of treatment leakage of oil and evaporated hydrocarbons. Low boiling point hydrocarbon leaks can possibly lead to fires and explosions in the unit. Crude Oil Low boiling point hydrocarbons may leak from improper connections between furnace, Distillation heat exchangers and distillation column. When the hydrocarbon leaks find any source of ignition, a fire or an explosion may occur. Thermal cracking is the source of coke formation which may block lines and connections leading to over-pressurizing and sometimes unit failure and consequent shut down. Hydrotreating Fine particulates from crushed catalyst may result in a dust explosion. Hydrogen sulphide is present and can cause corrosion. A high operating temperature leads to coke formation on the catalyst. Hydrocarbon vapour is a volatile organic compound that is hazard when it escapes to the atmospheric. Precautions Scheduled maintenance is required to prevent salt fouling and corrosion.
Coke formation can be prevented by controlling the temperature and pressure. Relief valves should be provided and regularly inspected for overpressure.
Catalyst handling and loading must be carried out with care so that fine particles from crushed catalyst are not produced. Regular maintenance on equipments is required to avoid corrosion and coke formation. Flare system were installed to
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prevent hydrocarbon vapours from escaping to atmosphere by combust hydrocarbon vapours into water and carbon dioxide.
Fluid Catalytic Cracking (FCC)
The presence of this oil coating and spent catalyst together will cause explosion during contact with air in the regenerator. Hydro cyclones must be carefully operated, otherwise catalyst fines will be carried out over to the distillation column. These fines will be concentrated in the decant oil.
Catalyst handling and loading should be based on the standard operating procedure to prevent catalyst dust explosion. Oil coating the spent catalyst should be stripped out in the stripper section of the reactor before sending it to the regenerator.
b) Acrylonitrile Production Unit Table 9.3 below is the hazard analysis for the petrochemical plant to produce the acrylonitrile and precautions are recommended. Table 9.3: Hazard analysis and precaution steps in acrylonitrile production unit. Process Potential Hazards Both acrylonitrile and acetonitrile are Distillation process in flammable solvents. Distillation columns present a special safety hazard due to its separating large inventories of flammable solvents. acrylonitrile Disturbance during normal operation such and acetone as spark from by reboiler engine can cause fire or explosion. Precautions Keep low inventories of flammable solvent inside distillation column. Perform scheduled check-up and maintenance for reboiler and condenser.
Hot spots may form in the reactor. Low Scheduled maintenance is required Propylene Ammoxidation boiling point hydrocarbons released from to prevent corrosion and ensure that a leak may lead to a fire or an explosion. temperature and pressure are in reactor controlled. Besides, inspections for piping and connections should be done regularly to assure acrylonitrile production quality. Acylonitrile Storage Acrylonitrile may undergo Acrylonitrile polymerization can be polymerization. The polymerization properly inhibited by DO NOT: reaction is highly exothermic; the heat a. Contact with free radical
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released can lead to additional catalysts such as peroxides and polymerization accelerating to the point hydroperoxides. where it becomes out of control. b. Mixing with basic/alkaline Monomer can vaporize at elevated material such as sodium temperatures and can cause sufficient hydroxide, potassium hydroxide pressure to rupture storage vessels. and ammonia. c. Exposure to high energy radiation such as UV light, Xrays and gamma rays. 9.4 PEAR ANALYSIS An acronym that may be used when assessing the significance of the emergency events is 'PEAR', which stands for People, Environment, Assets and Reputation. The most possible incidents to be occurred in refinery and petrochemical plants are explosion, gas emission and liquid leakage. Table 9.4 below is the discussion on the consequences towards the people, environment, asset and reputation due to the particular incidents.
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Table 9.4: PEAR analysis for the possible incidents in RAPID plant. Incidents 1. Explosion People Fatalities to workers. The high pressure of the explosion can cause injuries such as rupture of internal air-filled organs, including the ear drums, lungs or intestines. Explosions frequently cause fires and these fires, human might be burn. Explosions and the fires can generate toxic gases that, when inhaled, can both burn the lungs and enter the bloodstream to injure the body internally. If explosive gas is released, 2. Gas might cause explosion. emission to surroundin Inhalation of toxic gas will cause respiratory irritation, g. dizziness, headaches and cancer. Environment Nearby river, sea will become polluted and thus pollute the drinking water. The toxic smoke release during the explosion will pollute the air. Assets Buildings, facilities will be destroyed. Loss of huge amount of money due to the destruction of assets. Possible insurance claims that might reaches millions by the injured/ dead workers family. Reputation Reputation of the industry tarnished. Investors will be reluctant to join in the venture. Difficulties in starting a new plant project due to a bad record. A massive investigation will be conducted, which consumes time. Loss employees due to bad reputation.
Contaminate the air. Vapors cloudiness in nearby residential area and workplace.
Might cause corrosion to the piping lines or other unit operations. Possible insurance claims by workers due to the chronic effect caused by the contaminated air. Money spends for maintenance.
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Toxic gas released will be inhaled by the animals and will cause to sudden death. Leakage toxic chemicals to the surrounding workplace will cause respiratory irritation, dizziness, headaches and cancer. Contaminate recreational water bodies. If liquid that is highly inflammable, might cause burning and explosion especially in daylight. Contaminate drinking water. Contaminate soil and ground water. Might cause corrosion to the piping lines or other equipment. Corrodes and damages the paint color of building. Possible insurance claims by workers due to the chronic effect caused by the contaminated water source. May decrease property value. Money spends for maintenance.
3. Leakage of liquid materials to surroundin g.
*PEAR Analysis is being delivered from the Design safety talk by Mr Shum Keng Yan, Safety Manager of Johnson Control.
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9.5 HEALTH ASPECTS In the process, the chemicals involved might cause a negative effect to health if an adequate safety measures are not taken. Table 9.4 tabulated the health impacts of some particular chemicals and its permissible exposure limits.
Table 9.5 Health impact of chemicals and its permissible exposure limits. Chemical Sour crude oil[7] Health impact Permissible Exposure Limits (OSHA) Eye irritant, skin irritant, abdominal TLV-TWA 50ppm cramping, vomiting, diarrhea, pneumonia, severe lung damage, respiratory failure. Potential effects target the Central Nervous system, liver and kidneys. Eye irritant, skin irritant, abdominal TLV-TWA 50ppm cramping, vomiting, diarrhea, pneumonia, severe lung damage, respiratory failure. Potential effects target the Central Nervous System, liver and kidneys. Eye and respiratory system irritant, affects TWA 1 ppm central nervous system, skin irritation, STEL 5 ppm dermatitis, depression, drowsiness, headache, anemia and leukemia. Burns, frostbite, chronic respiratory TWA 500 ppm conditions. Cause damage to the following organs: TWA 10 ppm/ 11 mg/m3 blood, kidneys, lungs, liver, mucous membranes, heart, cardiovascular system, upper respiratory tract, skin, eyes, central nervous system (CNS), thyroid. Hazardous in case of skin contact, eye TWA 20 ppm contact, ingestion, inhalation. Severe over- STEL 60 ppm exposure can result in death. Carcinogenic effects, mutagenic effects, TWA 2 ppm teratogenic effects. Severe over-exposure can STEL 10 ppm result in death.
Sweet crude oil[8]
Naphtha[9]
Propylene[10] Hydrogen Cyanide[11]
Acetonitrile[12]
Acrylonitrile[13]
*TLV = Threshold limit value TWA = Time weighted average
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9.6 ENVIRONMENT ENGINEERINGASPECTS 9.6.1 Introduction Malaysia has committed to the Kyoto Protocol and Copenhagen Declaration whereby we are to reduce 40 % of carbon emissions by year 2020. The idea is to achieve the stabilisation of greenhouse gasconcentrations in the atmosphere at a level that would prevent dangerous anthropogenic interference with the climate system. Hence, this RAPID plant has responsibility to identify the waste and implement suitable management on it in order to protect our future lovely land and also obey Kyoto Protocol & Copenhagen Declaration.
9.6.2 Solid Waste Management Solid waste generally refers to any garbage, sludge or other discarded or salvageable materials, including solid, liquid and semi-solid materials, resulting from industrial, commercial, mining and agricultural operations as well as from community activities
[14] [14].
Solid waste management refers to the scientific management of waste after generation, reuse, and recycling, up to treatment and disposal . The management of industrial solid waste
generated from the four plants in this RAPID project is important to avoid adverse impacts on human health and the environment. There are variety wastes that are generated from many of the refining processes, and petroleum-handling operations, as well as wastewater treatment. Both hazardous and nonhazardous wastes are generated, treated and disposed. The residual refinery wastes are typically in the form of sludges, spent catalysts, filter clay and incinerator ash. Treatment for these wastes included incineration, land treating off-site, landfilling onsite, landfilling off-site, chemical fixation, neutralization and other treatment methods [15]. The major solid wastes in this RAPID plant are the catalysts which have been used in the refinery plant, hydro-treating plant, fluid catalytic cracking plant and petrochemical plant. For instance, Nickel-Molybdenum used in the hydro-treating plant; SAPO-11
(silicoaluminophosphates) used in the fluid catalytic cracking reaction and lastly BismuthMolybdenum Oxide which is used in the acrylonitrile production plant. The particular treatment methods are suggested for the solids wastes generated from the 4 plants as shown in table 9.5 below.
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Table 9.6: Solid waste management suggested for the 4 plants. Refinery Plant Waste Treatment Methods * Oily sludge make up of refinery solid Improve recovery of oils from oily sludge by using wastes. current technologies to mechanically separate oil, water and solids. For example, belt filter presses, recessed chamber pressure filters, rotary vacuum filters, scroll centrifuges, disk centrifuges, shakers, thermal driers and centrifuge-drier combinations. By this, losses of oil to the effluent system can be minimized[15]. Prevent solids and oily wastes from entering drainage system. By using API oil/ water separator to separate the oils which are deposited on solid particle. Besides, reduce heat exchanger bundle cleaning solids by using antifoulants in cooling water [15]. Hydro-Treating Plant Waste Treatment Methods * The fuel gas and hydrogen sulphide off Sent to the sour gas treatment unit and sulphur gas stream. recovery unit. Fluid Catalytic Cracking Plant (FCC) Waste Treatment Methods * Coke is collected on the catalyst surface. The catalyst needs to be regenerated continuously or periodically essentially by burning the coke off the catalyst at high temperatures. Long-life catalysts is used and regenerated to extend the catalysts life cycle. Catalyst dust consisting primarily The catalyst dust is carried with the CO stream to the alumina is produced from the fluid CO burner. The catalyst dust is then separated from catalytic cracking unit. the resulting CO2 stream via high efficiency two-stage cyclones and electrostatic precipitators and is sent offsite for disposal or treatment [15]. Petrochemical Plant Waste Treatment Methods * Since the cyclone system is not 100 % Electrostatic precipitator is suggested to be used after efficient, a certain amount of catalyst the cyclone separator to trap the residue catalyst fine.
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used in the fluid bed reactor is entrained in the off-gas and captured in the quench system. The loss is in the range of 0.30.7 kg/t acrylonitrile. * The treatment methods was reviewed and agreed by Mr Shum Keng Yan, Safety Manager of Johnson Control on 29th November 2012, at Department of Chemical Engineering, University of Malaya.
9.6.3 Air Pollution Control Lessons from Prof.Nik Meriam binti Che Hassan, air pollution is defined as undesirable change in the physical, chemical or biological characteristics of the air that can harmfully affect the health, survival or activities of humans or other living organisms. The pollutants in the air originate from several sources, such as combustion from off-gases, burning of residues, fugitive emissions from storage tanks and vent streams. The admitted limits must regulated by norms regarding air quality by government. For example, permitted limits of hydrogen cyanide and acrylonitrile are 2 ppm and 10 ppm respectively[16], while the value of carcinogenics (benzene) is 5mg/Nm3. In this case, a major source of pollution may be the off-gas leaving the acrylonitrile absorber. Ensuring high recovery of nitriles is desirable, which can be realized by using lowtemperature water, as well as an efficient absorber design. The same techniques can be used to complete the incineration of other toxic liquid and solid residues. The storage and handling of acrylonitrile and intermediates requires specific safety and pollution prevention methods. Fugitive emissions due to leaks of vessels are limited because of low operating pressure, but the vents streams are treated by water scrubbing. Trace quantity of inhibitors, such as hydroquinone derivatives, are added to avoid losses and fouling through polymerization[16]. Besides, there is a massive amount carbon dioxide and nitrogen produced as the byproducts of acrylonitrile. Carbon dioxide gas will cause air pollution and increase greenhouse gas (GHG) concentration. Hence, amine scrubbing technology was applied. Carbon dioxide forms a weak chemical bond with the amine and is absorbed into the amine. Nitrogen exits through the top of the absorber and is sent to the stack. (For further explanation, please refer process description for acrylonitrile production)
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9.6.4 Wastewater Treatment Water discharge standards and limits are specific for each country. According to Malaysia's Environmental Law, ENVIRONMENTAL QUALITY ACT, 1974, the Malaysia Environmental Quality (Sewage and Industrial Effluents) Regulations, 1979, 1999, 2000: Allowable cyanide content according to standard A is 0.5 mg/l. As an example, Table 9.6 shows key parameters sampled for Malaysia Standards.
Table 9.7: Limits of emissions for discharge of wastewater.
The suggested wastewater treatment is a sequence of systematic treatment. Firstly, pretreatment is needed to remove floating solids through screening or oil separation method. Later on, primary treatment, secondary treatment and tertiary treatment will be conducted to remove dissolved heavy metals or inorganic. There are certain treatment such as ultrafiltration, ion exchange, reverse osmosis and others. However, all this technology consumes a lot of money; hence adsorption is the best choice for us. The suggested adsorbent is magnetic biochar activated carbon from coconut shell or application of carbon nano-tubes due to its high adsorption capacity and low purchasing cost.
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9.7 PLANT LAYOUT [17] 9.7.1 Basic Considerations A good arrangement of unit operationfor the RAPID plant is necessary so that: [15] a) Safety in the plant can be secured. b) Overall property damage for unwanted incident can be minimized. c) Easy operation and maintenance can be facilitated. d) Future expansion can be made as possible. e) Cost of a project can be reduced. f) Physical appearance of the plant can be enhanced.
For a process plant, generally the area is being categorized into two: process area and non-process area. The process area includes the plant area in which the control and operation processes takes place and only specific workers can enter the site. For instance, central control room, R&D laboratory, effluent treatment plant, tank farm (raw material, products and byproducts storage area), fire assembly point, process area and future expansion site. While for the non-process area, it is the area which usually most of the workers will be and is considered as a public area in the plant.
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9.7.2 RAPID Project Plant layout
Guard House Enter / Exit Gate
Route of production Safe Line Boundary
Blast Wall Route of Raw Material/ Product
Figure
9.2:
Plant
layout
for
the
production
of
acrylonitrile
form
the
refinery
of
sour
crude
oil.
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9.7.3 Justification[17,18] Plant layout is very important for a plant as it is related to the economical flow of materials, safety and health issues of the personnel around the site. Figure 9.2 is the plant layout for the RAPID plant. The layouts of the unit operations, plant utilities, administrative office, entrance / exit gates and so on are decided as the safety and health issues are taken into consideration. Below are some justifications of the plant layout:
1) Process Area The process area shall be located at the most convenient place for operating the process unit. For instance, the four plants: petroleum refining, hydro-treating, FCC and petrochemical plants; and also the control tower, maintenance centre, R&D laboratory, utilities unit and wastewater treatment plant. For the units, it will be separated by roads. Major roads will have a minimum width of 10 m, while the minor roads will have minimum width of 6 m. As the plant contains several process units, the minimum spacing between equipment on the two adjacent units shall be at least 20 m. (especially for unit which processes flammable fluids and may be operated independently). Equipments should also be arranged to minimize the piping runs and therefore, reducing the installation cost. A clear access ways having a minimum width of 600 mm should be provided between the equipments so that it is easy for the operators to access around.
2)Plant Utilities, PCP and RGT-2 The plant utilities, including the boiler, compressor, air storage tank; and power regeneration plant (PCP and RGT-2) are located besides the process area for ready supply of utilities. For instance, the PCP stands for Power/ Cogeneration (COGEN) plant which is also known as Pengerang Co-gen Plant, while RGT-2 is the LNG Re-gasification Facility (RGT-2 Terminal). Utility units should be grouped together in an area classified as nonhazardous, except where they are an integral part of a process unit. If process units need large quantities of utilities, it should be located on the side near the utility centre. Therefore, the piping network can be minimized to ease the process. This is economical feasible as the production cost can be reduced since the avoiding of complication of piping or the transportation network. Utilities area should be located.
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3) Control Room and Electrical Substation The control room and substation should be located as close as possible to the plant equipment, and at the same time maintains a minimum distance from viewpoint of noise and safety requirements. This is to allow the plant operators to command and view the whole system of under control. The safe distance for the control rooms/ substation to the process equipment surface is at least 15 m. The control room and substation should be located so as to minimize the length of electrical and instrument cables entering and leaving, and therefore reducing the installation and operating cost.
4) Fire Fighting Requirements Each of the individual process unit should be provided with sufficient open spaces, so that in any condition the fire trucks can be run and operated. The width of access way should be at least 6 meters. The process units which consist of large hazardous material storage tanks should desirably be located in outer area of the complex site. On top of that, high-pressure gas lines should not pass through a process area, or run within 30 m of important structures/ equipment without shutdown valve. This is to ensure that portions of piping within the process area can be isolated from the main gas line and depressurized in case of an emergency. Besides that, at least two remote emergency shutdown stations should be provided. The wastewater separator that handles the hydrocarbons should be spaced at least 30m from process unit equipment handling flammable liquids, and 60 m from heaters or other continuous sources of ignition.
5) Emergency Exit, Emergency Assembly Area& Guard Houses For Green Area 1 and 3, it will also serves as the emergency assembly area for the plant. The Green Area 2 and 4 in the other hand will be reserved as the future expansion parts for the plants. There will be four enter/exit routes; two is proximity to the port for the convenient of import and export of the raw materials, by-products and products, while the other two is proximity to the car park for the workers and visitors to access the plant. There are four guard houses which are located in each of the entrance/ exit gates to ensure a good security of the plant such as to prevent the outside thief and stranger from entering the plant without the visitor permit.
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6) Safe Line Boundary (Security Fence) To enhance the security of the plant process site, a fence should be build to separate nonprocess area and process area so that only the authorized personnel can enter the site. The minimum space between security fence and units boundary should be at least 20 m, and between security fence and equipment should be 30 m. However, in case there is a special unit such as flammable material storage with vapour release and toxic materials, the minimum space should be at least 60 m from site boundaries adjacent to centres of population (nonprocess area).Fire water pumps and equipment shall be sufficiently proximity to the processing, storage and loading areas, where a major fire could occur. Furthermore, the flare area is being surrounded by blast wall, as a safety features to prevent any possible explosion from happening and minimize the hurt that can bring to the personnel whenever there is an accident occurs.
7) Non-Process Area (Office, Canteen, Car park) The non process area is usually the centre of population in the plant, where most of the workers will be working there. It includes the administration office, service area, laboratories, warehouses, workshops and canteen. The administration office should be located at a safe place on the site in order to protect personnel from hazards, and preferably located near the entrance of plant and near the car park alongside the main road of the plant. The distance between adjacent office buildings should be located as close as possible, to saves the time and makes it convenient for the workers to move from a building to the other.
8) Storage Area For the storage area, it should be located as far away as possible from buildings which is occupied by personnel at the site, but should be located near the process area for ready operation of the feed stocks and product run downs. To minimize the length of the pipeline, the process unit to which the feed stock is charged first, should be located on the side near the feed stock tanks. While the process unit from which the final products are withdrawn, should be located on the side near the products tanks to minimize the length of the product run-down line.
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9) Loading and Unloading Area The loading and unloading area should be located on the corner of the site, and is capable for connection to public road directly. The area for road transport should also have an adequate space to provide access for filling, parking and maneuvring. On top of that, the area should also be downwind/ crosswind from process units and sources of ignition, based on the direction of prevailing wind to avoid fire/explosion. Flare/burn pit/furnace in the other hand, should be located at the end corner of the site with sufficient distance to prevent personnel hazard.
9.8 REFERENCES [1] Ray, T. The Increasing Importance of Health, Safety, and Environment. (2011). Retrieved 9 December 2012, from https://www-304.ibm.com/connections/blogs/1f062ee8-a76e-4e2b 9554819673462f3b/entry/the_increasing_importance_of_health_safety_and_e vironment5?lang=en_us. [2] Workplace condition. (October 2010). Retrieved 20 October 2012, from http://www.usamanufacturers.com/blog/how-to-ensure-safety-at-manufacturing-plants/ [3] Maintenance. (NA). Retrieved 20 October 2012, from http://www.wisegeek.com/what-isplant-maintenance.htm [4] Gas detector. (NA). Retrieved 20 October 2012, from http://en.wikipedia.org/wiki/Gas_detector [5] Firefighting system. (May 2005). Retrieved 20 October 2012, from http://www.eagle.org/eagleExternalPortalWEB/ShowProperty/BEA%20Repository/Rules &Guides/Current/141_FireFightingSystems/Pub141_FireFighting [6] Mohamed A. Fahim, T.A.A., AmalElkilani, Fundamentals of Petroleum Refining. 2010, Elsevier. [7] Crude sour oil. (January 2011). Retrieved 20 October 2012, from http://www.keyera.com/titanweb/keyera/keyera.nsf/AllDoc/69E379D61D8DD687872578 4D0060B03D/$File/crude%20oil%20sour.pdf [8] Crude sweet oil. (January 2011). Retrieved 20 October 2012, from http://www.keyera.com/titanweb/keyera/keyera.nsf/AllDoc/20F8858F41B6006F8725784 D0060B888/$File/crude%20oil%20sweet.pdf [9] Naphtha. (NA). Retrieved 20 October 2012, from http://www.collectioncare.org/MSDS/naphthamsds.pdf [10] Propylene. (2010). Retrieved 20 October http://www.airgas.com/documents/pdf/001046.pdf [11] Hydrogen Cyanide (January 2012). Retrieved 20 October 2012, from http://www.airgas.com/documents/pdf/002271.pdf 2012, from
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[12]
Acetonitrile. (September 2012). Retrieved 20 October 2012, from http://www.sciencelab.com/msds.php?msdsId=9927335 [13] Acrylonitrile. (September 2012). Retrieved 20 October 2012, from http://www.sciencelab.com/msds.php?msdsId=9922795 [14] Lal, B.S., P. M. Wealth from Waste: Trends and Technologies. (2011). TERI Press, The Energy and Resources Institute: India. [15] Cheremisinoff, N.P., Handbook of Solid Waste Management and Waste Minimization Technologies. (2003). Elsevier Science: USA. [16] Prof. Alexandre C. Dimian, P.C.S.B., Chemical Process Design: Computer-Aided Case Studies. (2008). Wiley. [17]Plant layout. (February 2011). Retrieved 21 October 2012, from http://kolmetz.com/pdf/ess/PROJECT_STANDARDS_AND_SPECIFICATIONS_layout _and_spacing_Rev1.0.pdf [18] klmtechgroup, Layout and Spacing (Project Standards and Specifications). (2011). Retrieved 21 October 2012, from http://kolmetz.com/pdf/ess/PROJECT_STANDARDS_AND_SPECIFICATIONS_layout _and_spacing_Rev1.0.pfd
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KKEK 4281 DESIGN PROJECT ACRYLONITRILE PRODUCTION FROM SOUR CRUDE OIL

FEASIBILITY REPORT (RAPID) GROUP 10

FEASIBILITY REPORT (RAPID) GROUP 10

Acrylamide, A dipronitrile 15%

ABS and SANS 15%

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Percentage of World Acrylonitrile Consumption in 2011

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World Oil Reserves by Region

Middle East 56%

North America 16%

Central & South Europe America 8% 1%

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Ethane 26% Others 2%

Figure 2.2: Feedstock for Olefins Production in Year 1992.[1]

Gas Oil Butane 7% 5% Propane 12%

Ethane 23% Others 1%

FEASIBILITY REPORT (RAPID) GROUP 10

Heavy Naphtha Less and contain more aromatic compound. 85-190[2]

Approximate Range,oC Major product

Olefins products Require less than heavy naphtha.

Aromatic products Require high operating

temperature of cracking furnace.

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CHAPTER 3: PRODUCTS AND CO-PRODUCT

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Figure 3.1 c: The Acrylonitrile Capacity Utilisation in China [9].

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Table 3.1: Planned Additions of Acrylonitrile Capacity [9].

.Furthermore, according to Asahi Kasei Chemicals, acrylonitrile demand in Asia

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Figure 3.4: Global Acrylonitrile Price Trend. [7]

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CHAPTER 4 TECHNOLOGY PROCESS ROUTES

Carbocation is longer lived and more selective than free

The catalysts used are typically

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Based on the table

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CHAPTER 5: PROCESS DESCRIPTION

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n-Pentane iso-Pentane n-Hexane iso-Hexane

18.71 9.82 17.05 19.39

FEASIBILITY REPORT (RAPID) GROUP 10

Cyclopentane Methylcyclopentane Cyclohexane Benzene Total

6.45 13.27 9.44 5.87 100.00