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PRODUCTION OF OLEFINS
23.2.2010
Metathesis
OCT
SHOP
Gas to liquid (GTL)
Syn-gas
Fischer-Tropsch
Methane to Olefins
Methanol routes
Methanol to propylene
Oxidative coupling of Methane
Dehydrogenation
Oxidative
Dehydrogenation
Catalytic Pyrolysis
Summaries of Gas to Olefins routes
Biomass
Waste recycling
CO2
Considerations regarding technologies: green ethylene, process energy consumption, process
CO2 production.
3
SC:
SEP:
SR:
HVC:
HVCs.
OCT:
LPG:
NAPHTHA:
FEM:
Composition by weight
Hydrocarbon
Average Range
Paraffins
30%
15 to 60%
Naphthenes
49%
30 to 60%
Aromatics
15%
3 to 30%
Asphaltics
6%
remainder
Crude oil is very diverse in composition
depending on the source
10
Paraffins=
Thecommonnameforthe
alkanehydrocarbons.
11
[3]
12
PD:
SC:
CC:
HP:
GS:
OD:
OU:
OM:
LPG:
17
GAS:
FP:
FT:
18
Natural gas
Natural gas is a gas consisting primarily of methane. It is found
associated with fossil fuels, in coal beds, as Methane Clathrates,
and is created by methanogenic organisms in marshes, bogs, and
landfills.
The by-products of natural gas processing include ethane, propane,
butanes, pentanes and higher molecular weight hydrocarbons,
elemental sulfur, and sometimes helium and nitrogen.
Acid gas = CO2 , SH2
NGL = Natural Gas Liquids
Tail gas = CO2 + leftover S-compounds from Claus process.
Dehydration = Remove water vapor using either the regenerable
absorption in liquid triethylene glycol (TEG), or a Pressure Swing
Adsorption (PSA) unit which is regenerable adsorption using a solid
adsorbent. [5]
19
Natural gas
20
SEP:
SR:
OC:
OD:
21
Methane hydrates/clathrates
ice-like combinations of
methane and water on
the sea floor, found in
vast quantities)
are a potential future
source of methane
MethaneHydratePhases
22
23
GAS:
FP:
FEM:
HG:
FT:
24
25
HG:
DH:
OU:
Hydrogenation
De-hydration process (e.g. methanol to olefins, methanol to propylene and ethanol dehydration)
Olefins Upgrading (conversion of C4- C10) to light olefins, e.g. Superflex, Propylur and Olefins Cracking.
26
Steam cracking
Steam cracking and its products have a
backbone status for many industrial sectors.
The worldwide demand and production of olefins
are higher than for any other chemicals.
In general, steam cracking plays a dominant role
in olefin production.[6]
27
29
Naphtha first enters the convection section of a pyrolysis furnace, and it is preheated to 650oC.
Naphtha is vaporized with superheated steam and is passed into long (1225 m), narrow (25 125 mm) tubes,
which are made of chromium nickel alloys.
Pyrolysis takes place mainly in the radiant section of the furnace. The tubes are externally heated to 750900oC
(up to 1100oC) by fuel oil or gas fired burners.
Naphtha is cracked into smaller molecules via a free-radical mechanism in the absence of catalysts.
The free radicals lead to the formation of light olefins in the gaseous state.
The hot gas mixture is subsequently quenched in the Transfer Line Exchangers (TLE) to 550650oC, or
sometimes lower to 400oC.
TLE will then be followed by a series of heat exchangers and temperatures can drop down to 300oC.
These heat transfer activities avoid degradation by secondary reactions and at the same time generate high
pressure steam for driving compressors, etc.
However, heat exchangers are prone to fouling and therefore need both scheduled and unscheduled shutdowns.
30
In the primary fractionation section, gasoline and fuel oil streams (rich in aromatics) are
condensed and fractionated.
While this liquid fraction is extracted, the gaseous fraction is desuperheated in the quench tower
by a circulating oil or water stream.
The gaseous fraction is then passed through four or five stages of gas compression with
temperatures at approximately 15100 C, then cooling and finally cleanup to remove acid gases,
carbon dioxide and water.
Most of the dilution steam is condensed, recovered and recycled. Products of this section are fuel
oil and BTX.
BTX = benzene, toluene and xylene.
A common problem with compression is fouling in the cracked gas compressors and after-coolers.
The build-up of polymers on the rotor and other internals results in energy losses as well as
mechanical problems. Wash oil and water are used to reduce fouling.
31
refrigeration
de-methanizer Distillation at low temperatures.
de-ethanizer Distillation at low temperatures.
and others
C2 compounds, or ethylene and ethane, separation often requires large distillation columns with 120180 trays and
high reflux ratios.
Steam cracking performance has improved considerably over time. Now steam crackers typically obtain:
32
Decoking
Decoking
High pressure steam and air are fed to the furnace while it is heated up to 880900 C, or even up to 1100 C.
Coke on the inner surfaces of the wall and tubes is either burned off, washed away with high pressure water or
removed mechanically.
Depending on the feedstocks, coil configuration and severity, decoking for steam cracking furnaces is required
every 14100 days on an average.
33
Catalytic and other alternative olefin technologies can process conventional or heavy
feedstocks and are therefore alternatives to conventional steam cracking.{2}
i)
ii)
34
35
Catalysts provide an alternative route to steam cracking with the use of lower activation energy for CC bonds rupture.
Most of the catalysts cannot withstand extremely high temperatures and pressures as in steam cracking.
Temperatures for the catalytic naphtha cracking processes are 150250 C lower than those for steam crackers.
Even if the same operating conditions as those of steam cracking are applied for catalytic cracking, the total olefin yield by LGs
catalytic pyrolysis technology is still enhanced by at least 15%.{2}
It produces more gasoline with a higher octane rating than steam cracking.
It produces byproduct gases that are more olefinic than those produced by steam cracking.
Coke formed during the cracking process is constantly removed by the catalysts.
The catalysts are decoked through exothermic catalyst regeneration with oxygen or catalyst decoking.
36
FCC Schema
Plant size has increased two orders of magnitude from 10,000 t/y (1945) to >1 000 000 t/y (2000).
Propene
Strong global demand for propene, presently outpaces supply from these conventional sources.
Propene is used for about 60% for making polypropene. The rest for producing acrylonitrile, oxo
alcohol and acrylic acid.
38
39
A few engineering firms have become the repositories of process technology for petrochemical
commodities.
Competitive forces drive these firms to continuously make incremental improvements in their
respective technologies, but not to replace them.
The metal upper temperature limit in the cracking furnace coils is a current limitation of the
technology that is difficult to overcome.
The ethylene furnace has undergone modifications to improve product value, energy recovery,
and capital cost but there has been no fundamental change in the way the ethylene is produced.
Any new process must demonstrate significantly better economics than the existing process.
Additionally, the process reliability, safety, and environmental performance of the new process
must be at least comparable to or superior to the existing process.
40
OM:
SC:
CC:
PD, DH, OD:
Olefin Metathesis.
Steam cracking.
Catalytic Cracking or Catalytic Pyrolysis.
Propane dehydrogenation, Dehydrogenation, Oxidative dehydrogenation.
41
Olefin metathesis
Derived from the Greek words meta (change)
and thesis (position), metathesis is the exchange
of parts of two substances.
In the reaction, AB + CD -> AC + BD
AB
+AB>BB+AA
42
R1
R1
R1
R2
R2
R2
R2
Calderon
R2
R2
R2
R2
R1
R1
R1
R1
R
R
Grubbs
43
R1
[M]
R1
(a)
R1
R1
[M]
R1
R1
M
R1
(b)
R1
R1
[M]
R1
R1
Catalysts development
45
Catalysts development
46
47
MgO
catalyst
48
Production of 1-hexene
A semi-works unit using the OCT (olefins
conversion technology) process is used at
Sinopecs olefin plant in Tianjin (China), for the
metathesis of butene to produce 3-hexene,
which is then isomerized into 1-hexene
(comonomer used in the production of
polyethene).
+
Isomerization
49
50
51
52
Methane-rich gases are converted into liquid fuels either via direct conversion or via
syngas as an intermediate, for example using the Fischer-Tropsch.[8]
53
Naturalgas
Airseparation
Gasseparation
O2
Methane
Syngasproduction
(LPG)Liquid
Petroleum
Gas
COH2
FischerTropschprocess
MixedLiquidHydrocarbons
Separationprocesses
Cracker
Naphtha+Wax
Light
olefins
Ethylene
Dehydrogenation
OfEthane,
Propane
Propylene
54
i)
Steam reforming.
ii)
iii)
Autothermal reforming.
iv)
One of the biggest challenges is to optimize the energy integration between the
syngas generation and syngas conversion sections.
55
Steam reforming
An obvious advantage of steam reforming is that its does not need an oxygen plant.
At high temperatures (700 1100 oC) and in the presence of a metal-based catalyst (nickel), steam reacts with
methane to yield carbon monoxide and hydrogen.
Additional hydrogen can be recovered by a lower-temperature gas-shift reaction with the carbon monoxide
produced.
The hydrogen must be separated from the CO2 to be able to use it.
This is primarily done by Pressure Swing adsorption (PSA), amine scrubbing and membrane reactors
H = + 206,2 kJ/mol
H = -41,2 kJ/mol
56
ii.
The non-catalytic partial combustion of methane produces syngas with a H2/CO ratio (<2) close to the optimum
needed by the FischerTropsch synthesis.
This low H2/CO ratio gas results from the very little, if any, steam that is used in the process.
CH4 + O2
->
CO + 2 H2
H = -35,7 KJ/MOL
Due to the absence of catalyst, the reformer operates at an exit temperature of about 1400 C.
57
iii.
The syngas is soot-free and less ammonia and HCN are produced as compared to a POX.
However, at a Steam/Carbon ratio of 1.3 the syngas will have a H2/CO ratio of about 2.5, which is higher than the
ratio needed by the FischerTropsch section.
iv.
Autothermal reforming
Combined reforming
58
Fischer-Tropsch process
Synthesis gas (syngas = carbon monoxide and hydrogen), is converted into liquid hydrocarbons of
various forms.
The most common catalysts are based on Fe and Co (Ni and Ru have also been used).
(2n+1)H2
nCO
->
CnH(2n+2)
nH2O
Most of the alkanes produced tend to be straight-chained, although some branched alkanes are
also formed.
In addition to alkane formation, competing reactions result in the formation of alkenes, as well as
alcohols and other oxygenated hydrocarbons.
Usually, only relatively small quantities of these non-alkane products are formed, although
catalysts favoring some of these products have been developed.
59
Fischer-Tropsch process
CO
->
H2
CO2
It should be noted that, according to published data on the current commercial implementations of
the coal-based Fischer-Tropsch process, these plants can produce as much as 7 tons of CO2 per tons of liquid
hydrocarbon products (excluding the reaction water product).
This is due in part to the high energy demands required by the gasification process, and in part by the design of
the process as implemented.
Higher temperatures lead to faster reactions and higher conversion rates, but also tend to favor methane
production.
Increasing the pressure leads to higher conversion rates and also favors formation of long-chained alkanes both of
which are desirable.
Chemically, even higher pressures would be favorable, but the benefits may not justify the additional costs of highpressure equipment.
60
61
Olefins (e.g., ethylene and propylene) can also be produced from natural gas (i.e.,
methane) via: - Methanol
- Oxidative coupling routes
Methane-based routes use more than twice as much process energy than state-ofthe-art steam cracking routes do (the energy content of products is excluded).
There are two types of C1 routes through which natural gas can be converted into
olefins:
Indirect routes (via syngas or ethane)
Direct routes (directly from methane to light olefins).
This route is technically difficult because of low selectivity to light olefins and high
yield of heavy hydrocarbons.
Today, the chemistry of the direct route remains one of the worlds major scientific
challenges while there are very few publications currently available on the topic.
62
OC:
DH:
PD:
OD:
Oxidative Coupling
Dehydrogenation
Propane Dehydrogenation
Oxidative Dehydrogenation
63
i)
-
ii)
->
->
H3C-CH3
H2C=CH2
->
H2C=CH2
+
H2
H2
(several other processes possible)
The catalysts used are mostly oxides of alkali, alkaline earth and other rare earth metals.
After one pass, roughly 80% of the total oxygen feed by mass is consumed.
The per-pass ethylene yield on a mass basis of methane is about 30%. [9]
64
The current performance of OCM routes in terms of energy use is poorer than that of state-of-theart steam cracking primarily due to the following problems:
i)
Low yields.
There is a trade-off between methane conversion and selectivity to ethylene.
Under 600 oC, the rate of reaction is slow, but above 600 oC undesired oxidations dominate the
reactions.
ii)
Separation.
Relatively high energy use in separation and recycling.
iii)
Catalysts.
Additional oxygen and hydrogen are required for reducing coking on catalysts.
High temperatures at 7501000 oC require catalysts with high thermal stability.
iv)
-
Other issues,
Possible explosion due to the mixture of oxygen and hydrocarbons.
CO and CO2 emissions, aromatic hydrocarbons, acid gas and organic acid.
Operability. [9]
65
Dehydrogenation of Ethane or
Propane [10]
If the CO2 emissions from oxygen usage are included, the total CO2 emissions is 15%
higher than that for ethane cracking.
H3C-C3H + O2 -> H2C=C2H + H2O
H2 O
* Ethylene yield from steam cracking of propane is up to 45% and propylene yield is
12%.
66
Oxidative dehydrogenation
ODH is Exothermal.
Dehydrogenation and Cracking are Endothermal.
Process simplicity.
(a) The combination of exothermal alkane combustion with the
endothermal dehydrogenation, at temperatures higher than 700 oC.
The use of O2 enables to overcome thermodynamic limitations and
to avoid catalyst regeneration.
(b) A true ODH occurring with redox-type catalysts already at
temperatures lower than 500 oC. Amongst the catalysts used, the
most investigated ones are those based either on vanadium oxide or
on molybdenum oxide.
67
GAS:
FP:
FEM:
HG:
FT:
68
69
Biomass Gasification
70
Char: is the solid material that remains after light gases (e.g. coal gas) and tar (e.g. coal tar)
have been driven-out or released from a carbonaceous material, during the initial stage of
combustion, which is known as carbonization, charring, devolatilization or pyrolysis.
71
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This reaction is limited because selective transfer of the relatively high depolymerization enthalpy
to the reactants is difficult.
Not only polymer generated in situ, but also normal commercial polyethylene was degraded in the
same way.
In this context Dufaud and Basset have succeeded in activating the C-C bond in PE catalytically
with a strongly
Electrophilic Ziegler - Natta catalyst and cleaving it by the action of hydrogen at 150 oC.
Initially oligomers were formed which were then further cleaved to lower alkanes.
Formally regarded this is a statistical chain cleavage which, because of the involvement of
hydrogen, may even be considered to be a retro-polycondensation.
Never the less, this discovery is remarkable since for the first time a catalyst has been found that
is actively involved in the primary reaction.
74
Thermal depolymerization
(TDP) is a process using
hydrous pyrolysis for the
reduction of complex organic
materials (usually waste
products of various sorts, often
known as biomass and plastic)
into light crude oil.
[12]
76
77
HG:
DH:
dehydration)
OU:
Olefins Cracking.
Hydrogenation
De-hydration process (e.g. methanol to olefins, methanol to propylene and ethanol
Olefins Upgrading (conversion of C4- C10) to light olefins, e.g. Superflex, Propylur and
78
CO2 recycling
How to collect the CO2?
Carbon dioxide scrubbing based on potassium carbonate exists.
- Single Step methods: CO2 + H2 Methanol, green methanol
- Single Step methods: CO2 Hydrocarbons
- 2 Step methods: CO2 , CO Hydrocarbons
If CO2 is heated to 2400oC, it splits into carbon monoxide and
oxygen.
The Fischer-Tropsch process can then be used to convert the CO
into hydrocarbons.
79
CO2 - Methane
80
Any
available
energy
source
(alternative
energies
such as
solar, wind,
geothermal,
and atomic
energy) can
be used for
the
production
of needed
hydrogen
and
chemical
conversion
of CO2.
81
Catalytic Hydrogenative
Conversion of Carbon Dioxide to
Methanol
CO2
3 H2
->
CH3OH
H2O
This reaction has been known to chemists for more than 80 years. In fact,
some of the earliest methanol plants operating in the U.S. in the 1920-1930s
commonly used carbon dioxide for methanol production.
A)
->
3 H2
2 H2
->
H298K =
CH3OH
3 CH4
CO2
- Steam reforming
2 CH4
2 H2O
- Dry reforming
2 CH4
CO2
- Bireforming
3 CH4
2 H2O +
B)
H2O
C)
Photohydrogen
- Biological hydrogen production from Algae and Bacteria.
- Photoelectrochemical cell.
->
17.9 kcal/mol
H2O
CH3OH
2 H2O
2 CO
6 H2
3C
- Bireforming
e-
->
->
->
2 CO
CO2
H2
+
->
O2
2 H2
4 CO
H298K =
8 H2 ->
4 CH3OH
68.3 kcal/mol
83
Bio-mass
Bacteria(Clostridiumacetobutylicum)
BioButanol
BioEthanol
Processchemistry
GreenButanol
1)Hydrolyticconversion.
Biooils
2)Decarboxylation.
GreenButanol
3)Reforminglongchainalkanes.
84
Ethanol to butanol
85
Conclusions
Energy use and CO2 emissions in all C1 routes are much higher than
those of steam cracking.
Methane-based routes use more than twice as much process
energy than state-of-the-art steam cracking routes do.
Methane based routes lead to 6085% more CO2 emission than the
state-of-the-art ethane cracking.
Among the methanol-related routes, UOP MTO is the most efficient,
but its energy use is still about 150% higher compared to state-ofthe-art naphtha-based steam cracking.
Methanol-related routes have similar energy use, but cause slightly
higher CO2 emissions than DSM OCM I and II do.
86
Conclusions
By conducting a comparative analysis of the energy use, CO2
emissions and production costs of C1 technologies and steam
cracking, we found that methane-based routes use more than twice
as much than process energy than state-of-the-art steam cracking
routes do (the energy content of products is excluded).
Oxidative coupling routes are currently still immature due to low
ethylene yields and other problems.
The methane-based routes can be economically attractive in
remote, gas-rich regions where natural gas is available at low prices.
The development of liquefied natural gas (or LNG) may increase the
prices of natural gas in those locations.
While several possibilities for energy efficiency improvement do
exist, none of these natural gas-based routes is likely to become
more energy efficient or lead to less CO2 emissions than steam
cracking routes do.
87
Sources
[1] The Compelling Facts About Plastics, An analysis of
plastics production, demand and recovery, for 2005 in
Europe - Published Spring 2007
[2] Galli, Journal of Polymer Science, Part A, Polymer
Chemistry, 42 (2004), 396-415
[3] en.wikipedia.org/wiki/Crude_oil
[4] http://en.wikipedia.org/wiki/Coal
[5] http://en.wikipedia.org/wiki/Natural_gas
88
Sources
[6] Ren T., Patel M., Blok K., Energy (Amsterdam
Netherlands) (2005) Volume Date 2006 31(4) 425-451,
Olefins from conventional and heavy feedstocks, Energy
use in steam cracking and alternative processes.
[7] Refs\Belgiorno V., De Feo G., Della Rocca C., Napoli
R.M.A., Waste Management (Amsterdam Netherlands)
(2003) 23(1) 1-15, Energy from gasification of solid
wastes.pdf
[8] en.wikipedia.org/wiki/Gas_to_liquids
[9] Ren T., Patel M.K., Blok K., Energy (Oxford United
Kingdom) (2008) 33(5) 817-833, Steam cracking and
methane to olefins, Energy use CO2 emissions and
production costs
89
Sources
[10] Ren T., Patel M., Blok K., Energy (Amsterdam
Netherlands) (2005) Volume Date 2006 31(4) 425-451,
Olefins from conventional and heavy feedstocks, Energy
use in steam cracking and alternative processes.
[11] Refs\Belgiorno V., De Feo G., Della Rocca C., Napoli
R.M.A., Waste Management (Amsterdam Netherlands)
(2003) 23(1) 1-15, Energy from gasification of solid
wastes.pdf
[12] Newborough M., Highgate D., Vaughan P., Applied
Thermal Engineering (2002) 22(17) 1875-1883, Thermal
depolymerization of scrap polymers.pdf
[13] www.sunbayenergy.com/faq_plasma.html
90