CN101134700B - Method For The Decomposition of Methyl Tertiary-Butyl Ether - Google Patents

11/9/2018 CN101134700B - Method for the decomposition of methyl tertiary-butyl ether - Google Patents
Patents
Method for the decomposition of methyl tertiary-butyl ether
Abstract
CN101134700B
A process for the dissociation of methyl tert-butyl ether (MTBE), which includes at least a) catalytic
CN Grant
dissociation of MTBE which is present in two streams I and VII over a catalyst to give a dissociation
product II, b) separation by distillation of the dissociation product II obtained in a) into an overhead
stream III containing more than 90% by mass and a bottom stream IV containing diisobutene, MTBE Download PDF Find Prior Art Similar
and more than 80% of the methanol present in the dissociation product II, c) separation by
distillation of the bottom stream IV obtained in b) into a methanol-containing bottom stream V, a Other languages: Chinese
sidestream VI containing diisobutene, methanol and MTBE and an overhead stream VII containing
Inventor: D·马施迈耶, F·尼尔利克, H·-W·詹托夫, M·温特伯格, S·S·
MTBE and methanol and d) recirculation of the overhead stream VII to a).
弗南德茨, S·侯布里克茨, W·卢哈, W·布施肯
Original Assignee: 赢创奥克森诺有限责任公司

Classi cations
Priority date : 2006-08-29
C07C1/20 Preparation of hydrocarbons from one or more compounds, none of them being a
hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms Family: US (1) EP (1) JP (1) KR (1) CN (1) DE (1)
View 2 more classi cations

Date App/Pub Number Status
2006-12-22 CN 200610168673
2008-03-05 CN101134700A Application
2012-08-08 CN101134700B Grant
Info: Patent citations (8), Cited by (18), Legal events, Similar

documents, Priority and Related Applications
External links: Espacenet, Global Dossier, Discuss
Claims (8) translated from Chinese
1. 1. A method for methyl tert-butyl ether (MTBE) decomposition, the method comprising at least the following steps: a) on the catalyst present in the catalytic
decomposition of MTBE at re ux stream VII comprising MTBE feed stream I and a composition comprising of MTBE to obtain a mixture containing isobutene, methanol,
MTBE diisobutylene and decomposition products II, B) the decomposition product of step a) is obtained in the distillative separation II containing more than 90% by mass
of isobutene overhead stream III and containing diisobutene, MTBE and methanol contained in the bottom stream IV in the decomposition product II higher than 80%, c)
the bottom stream IV distillative separation step b) is obtained as bottoms stream comprising methanol V, containing diisobutene, methanol and MTBE sidestream VI
and VII overhead stream comprising MTBE and methanol, and d) an overhead re ux stream VII to step a).
2. 2. The method of claim I, wherein the separated 2-methoxybutane with the side stream VI.
3. The method of claim I or claim 2, wherein step b) is that the decomposition of MTBE was carried out at higher conversion conditions 2- methoxybutane
conversion.
4. 2-methoxybutane decomposition activity is at least 1-3 of at least one process of claim 1, wherein the decomposition step a) is performed on the catalyst, the
catalyst decomposition activity than MTBE 1%.
5. The method of claim 3, wherein the decomposition step a) is carried out in a single pass conversion of 50 to 98% of MTBE.
6. 1-5 at least one of claim 1, wherein the industrial use of MTBE as stream (I).
7. 1-6 to at least one of claim 1, wherein, containing C4 and / or C5 hydrocarbon feed MTBE (Ia) in the pre-separation column (K3) containing the (; and / or C5
hydrocarbons of the overhead stream (VIII) and freed of containing said C4 and / or MTBE bottoms product containing C5 hydrocarbons, wherein the bottoms
product or separately from the re ux stream (VII) mixture as stream ( I) R is introduced into the reactor.
8. The method of at least one of claim 1-7, characterized in that the overhead stream containing isobutene in a further method step f) obtained from the process
step b) (III) isolated by extraction with methanol dimethyl ether and water and separated by distillation.
Description translated from Chinese
The method of decomposition of methyl tertiary butyl ether
Technical Field [0001] The present invention relates to a method of preparing isobutene by decomposing methyl-tert-butyl ether (MTBE).
Background technique
[0002] isobutylene for the production of many products (e.g. the production of butyl rubber, polyisobutylene, isobutylene oligomers, branched C5 acids, C5 carboxylic
acids, alcohols and C5 ole ns C5) starting material. In addition, the alkylating agent is also used as isobutylene Synthesis of tert-butyl aromatic compounds and
peroxides produced as an intermediate product. Further, isobutylene can be used as a precursor for preparing methacrylic acid and its esters.
[0003] isobutylene often coexist with a saturated or unsaturated C4 hydrocarbon stream in Ester industry. Due to the low boiling point difference between isobutene and
butene I- or very low separation factor can not be separated economically by distillation from the mixture and isobutene. Thus, a isobutene from a hydrocarbon mixture
https://patents.google.com/patent/CN101134700B/en 1/21
usually carried out by Ester industry, i.e., the conversion of isobutene is easily separated from the other derivatives of the remaining hydrocarbon mixture, which was then
separated and isobutene derivative derivatized decompose back together again ϋ .
[0004] Generally, (e.g. a steam cracker C4 fraction) was separated from the C4 fraction of isobutene in the following manner. After passing through the extraction
(extraction distillation) or selective hydrogenation to linear butenes to remove most of the polyunsaturated hydrocarbons (mainly Ni but-ene), the remaining mixture
(ra nate I or hydrogenated cracking C4) and alcohol or water of reaction. When using methanol to obtain methyl tert-butyl ether (MTBE) from isobutylene, tert-butanol to
give (TBA) when water is used. After their separation, both products can be reversed in their formation process is divided into isobutene.
[0005] with respect to the PBA more valuable in terms of MTBE, because hydrocarbon-containing isobutylene is reacted with methanol to more easily reacts with water,
and MTBE as a gasoline component and mass production. So get isobutylene and then get more compared to the potential economic value of isobutene from TBA, if
similar good method for decomposing MTBE and TBA decomposition are possible from MTBE.
[0006] MTBE decomposition may be carried out in the presence of an acidic catalyst in the liquid phase, gas-liquid or gas phase. No matter what phase of decomposition
in both by-products, although in different degrees. Such as isobutylene generated from the acid-catalyzed decomposition of ni by polymerization or oligomerization
reaction may form undesirable components C8 and C12 components. C8 undesirable mainly refers to 2,4,4-trimethyl-1-pentene and 2,4,4_-trimethyl-2-pentene, known as
Ni below isobutylene (DIB). Further, part of the methanol decomposition of the methyl ether can be converted into Ni.
[0007] The reasons (low cost, high availability and easy) economic, prepared for purposes of isobutene by the decomposition of MTBE, without the use of high-purity
MTBE (e.g. Oxeno Olef inchemieGmbH of MTBE / S), but the use of common industry Ester quality (fuel quality) MTBE. Ester industry mainly containing MTBE C8 ole ns
as by-products, such as 2-methoxybutane mentioned above (formed from linear butenes and methanol in the synthesis of MTBE), of TBA, methanol and C4 hydrocarbons
and optionally C5 hydrocarbons .
[0008] MTBE must be entrained by the starting components and secondary components generated during the decomposition is separated from the isobutene and / or
re ux stream out, so that most Ester Arts costs (of investment, operating costs) assessed in post-processing section.
[0009] Various methods known in the preparation of isobutene by MTBE decomposition.
[0010] In the column by the decomposition of MTBE was stirred reactor, distillation columns, extraction columns and consisting of isobutene prepared by EP 0302336.
Acidic catalyst provided in the bottom cycle. MTBE was fed into the bottom cycle. Loop portion of the bottoms are discharged. The crude isobutene in the column was
extracted with water. The aqueous methanol extract containing extracted above the bottom. As an overhead product containing isobutene. Bottoms discharged was
re uxed in part after extraction amount.
[0011] The method of claim ー protected species in EP 0068785, the decomposition of MTBE in the process carried out in a continuously operated stirred tank. An acidic
catalyst is suspended in the starting material. Isolated from the reaction mixture was distilled off isobutene column as an overhead product. A portion of the bottom
product back into the stirred tank. In other parts of the double column separation system is returned to the stirred vessel and the MTBE-containing stream is withdrawn
as a side stream of methanol. The document does not disclose how to separate the minor component used in MTBE and the by-product formation.
[0012], MTBE decomposition in the reactive distillation column in DE 3210435. Obtained as overhead product and a trace amount of methanol ni isobutene mixture
containing isobutene. The bottom product of the reactive distillation column is separated is returned to the reactive distillation column and a stream containing MTBE
bottoms product in a methanol fractionator. This document does not explain how byproducts separation.
[0013] 0633048, DE 10020943 and DE 10111549 require the document EP protected prepared by the reaction of isobutene in MTBE decomposition distillation column.
There is no disclosure secondary components separated from the decomposition products.
[0014] describes a method of preparing isobutene by MTBE decomposition in the gas phase in DE 10227350 and DE 10227351. In both methods, the decomposition
product was extracted with water and concentrated. As the aqueous extract obtained - methanol mixture, and the mixture was distilled to separate methanol and water.
The ra nate from isobutylene, MTBE and unconverted secondary component. This mixture was separated by distillation contains a small amount of Ni ether and
isobutylene overhead product and a bottoms product consisting of MTBE and secondary components. Described on the application of MTBE and workup of the resulting
mixture is no clari cation.
[0015] In particular US 6049020 discloses the preparation of isobutene by the decomposition of MTBE. Methanol is removed by extraction with water from the reaction
product. Remaining ra nate is separated by distillation as a bottom product containing MTBE and minors isobutene overhead product and the unconverted thereof. No
workup described MTBE mixture. Carried out after the decomposition products similar process in US 6072095 and US 6143936. MTBE mixture containing the secondary
components obtained without a post-treatment, this mixture can not be supplied to the apparatus for preparing MTBE.
[0016] In the known preparing isobutene by MTBE decomposition method, since the high cost of separating the by-product and give MTBE untransformed. MTBE stream
containing by-products after the discharge portion is returned to the amount of MTBE decomposition reaction apparatus is connected upstream and / or to the. In each
case the yield of isobutylene and isobutylene-based device is supplied to the reduction of MTBE meter.
SUMMARY
[0017] Accordingly, the object of the invention is to provide an alternative method of preparing isobutene from MTBE ー species, in particular to improve or simplify the
post-treatment of the bottom product obtained during distillation separation of the decomposition product by this method.
[0018] It has now surprisingly been found that if such bottoms product only ー additional distillation step is separated into a bottom stream containing methanol,
containing isobutene ni, side stream containing methanol and MTBE MTBE and the overhead product and the overhead product is returned to the decomposition reaction
of methanol in the post-processing can be simpli ed in the bottoms product during distillation separation of the resulting decomposition products. When the content of
2-methoxybutane MTBE in the feed, then the portion of 2-methoxybutane be discharged via the side stream.
[0019] Accordingly, subject of the present invention is a method for decomposing methyl-tert-butyl ether (MTBE), the method comprising at least the following steps:
[0020] a) catalytic dissociation of MTBE over a catalyst contained in the two streams I and VII to obtain a decomposition product II,
[0021] b) step a) decomposition product obtained in the distillative separation II containing more than 90% by mass of the isobutene-containing overhead stream and III
ni isobutylene, MTBE and more than 80% of the decomposition products contained in II, methanol bottom stream IV,
[0022] c) step b) obtained in the separation by distillation bottom stream containing methanol IV bottoms stream V, Ni containing isobutene, methanol and MTBE and a
side stream VI comprising MTBE and methanol overhead stream VII, and
[0023] d) the overhead stream VII returned to step a)
[0024] advantages of the present invention is that the process is not isolated Ester arts ni isobutylene may be desirable only ー distillation step in a simple manner.
Another advantage that may be discharged ー 2-methoxybutane with MTBE feed entrained with ni isobutylene and butene content thereby limiting isobutene straight
chain. In addition, separated in step c) is pure methanol, such that it can be used for most industry Ester synthesis, for example esteri ed or etheri ed. In addition to low
investment, other advantages of high yields of isobutene, based on the feed to MTBE meter apparatus. If isobutylene is not a part of the device set of production
equipment (e.g. C4 with MTBE synthesis after treatment), but the use of MTBE feed device (standalone device), such an advantage is particularly large.
[0025] The following example describes the present invention but are not to limit the invention to this, the scope of the present invention is de ned by the claims and the
description given. Claims also belong to the present disclosure. If the range given below, or a compound of general formula type, the disclosure includes not only the
corresponding ranges or groups of compounds are explicitly mentioned, but also all part of the range of compounds may be obtained by deleting individual values
(ranges) or compounds and part of the group, in order to more clarity is not explicitly stated.
[0026] wherein the method for methyl tert-butyl ether (MTBE) decomposition of the present invention in that the method comprises at least the following steps:
[0027] a) catalytic dissociation of MTBE over a catalyst contained in the two streams I and VII to obtain a decomposition product II,
[0028] b) step a) decomposition product obtained in the distillative separation II containing more than 90% by mass of the isobutene-containing overhead stream and III
ni isobutylene, MTBE and more than 80% of the decomposition products contained in II, methanol bottom stream IV,
[0029] c) step b) obtained in the separation by distillation bottom stream containing methanol IV bottoms stream V, Ni containing isobutene, methanol and MTBE and a
side stream VI comprising MTBE and methanol overhead stream VII, and
[0030] d) the overhead stream VII returned to step a).
[0031] Method step a)
[0032] The presence of a mixture of MTBE decomposition re ux stream (VII) ⑴ composition containing feed stream containing MTBE and the MTBE in the method step
a). We will be present in the stream (I) and (VII) of MTBE and methanol can be decomposed into isobutene in the liquid phase or mixed phase gas / liquid in the presence
of an acidic catalyst or in the gas phase. In the MTBE decomposition process of the invention is preferably carried out at 120-450 ° C in the gas phase. Preferably, MTBE
decomposition, MTBE, particularly when using an inorganic catalyst in the decomposition at 200-400 ° C, preferably 230_350 ° C.
[0033] In the method of the present invention, MTBE may be used in order to decompose all known acidic catalyst for the decomposition of MTBE. Can be used as an
acid catalyst, for example, metal oxides, mixed metal oxides, particularly those containing Ni or silicon oxide, or a metal salt of an acid on a metal oxide support of
alumina.
Decomposition [0034] Preferably, in step a) is carried out on a catalyst, the catalyst for the decomposition of MTBE higher than for active 2-methoxybutane decomposing
activity at least 1%, preferably 5%, and particularly preferably 10 %. Activity of the catalyst can be measured in a simple manner, i.e., the mixture of MTBE and MSBE under
stable conditions over a catalyst selected, and then the resultant reaction product was analyzed based on MSBE and unreacted MTBE.
[0035] Preferably, the decomposition of MTBE, preferably using a catalyst for the dissociation of MTBE formally made of magnesium oxide, aluminum oxide and silicon
oxide ni process of the invention in the gas phase. These catalysts are described in US 5171920, for example, Example 4, and EP 0589557.
[0036] Particularly preferred is the use form comprising magnesium oxide, aluminum oxide and silicon oxide catalyst is Ni, and the share of magnesium oxide catalyst O.
5-20% by mass, preferably 5-15% by mass, and particularly preferably 10-15 mass%, 4-30 mass% share of alumina, preferably 10-20% by mass, Ni and silicon oxide 60 to
95% by mass share, preferably 70-90% by mass. When the addition of magnesium oxide catalyst further contains an alkali metal oxides
oxide may be advantageous. The alkali
metal oxide may be selected, for example, Na2O or K20. Preferably, the catalyst contains alkali metal oxides
oxide Na2O. Preferred catalysts employed preferably have 200-
450m2 / g, more preferably 200-350m2 / g BET surface area (DIN ISO 9277 was measured in accordance with the volume of nitrogen). If the catalyst of the present
invention is applied to the carrier as an active material, then only the active material has a BET surface area of the range. In contrast, a catalyst and a carrier material
having a BET surface area signi cantly from the support according to the properties, especially having a BET surface area smaller.
[0037] The pore volume of the catalyst is preferably O. 5-1. 3ml / g, preferably O. 65-1. Lml / g. The pore volume is preferably determined by the method of cyclohexane. In
this method, a test sample is rst dried to constant weight at 110 ° C. Then about 50ml accurately weighed sample O. Olg charged to the cleaned and dried to a constant
weight of the dipping tube, the impregnated tube has a lower side with a ground ro ro discharge cock. The sheet covered with a small outlet ko alkenyl made from
polyethylene sample to prevent clogging of the discharge ro. After lling a sample tube dipping, carefully hermetically sealed the tube. The tube is then impregnated with
a water-jet pump is connected, via the open mill ro tap water and the degree of vacuum in the impregnation tube was adjusted to 20mbar. It can detect the degree of
vacuum gauge connected in parallel through. After 20 minutes, close the stopcock grinding ro, then dipping the evacuated tube is pre-loaded with the accurate
measurement of cyclohexane wherein the receiver volume of cyclohexane is connected, so that by opening the cock ro ro mill cyclohexyl alkoxy dipping pumped from the
receiver tube. The grinding ro ro cock remains open until the entire sample is immersed cyclohexane. And then closed again grind ro cock. After 15 minutes, the
impregnated tube is carefully placed cyclohexane and air discharge is not absorbed into the receiver. Adhering the impregnated tube or a discharge pressure ka careful
impact connecting portion or the mouth of the receiver with cyclohexane, cyclohexane can be fed through the suction ball to a receiver via the air conduit. Record the
volume of cyclohexane present in the receiver. Volume of cyclohexane absorbed by the pore volume divided by the mass of test sample given the volume of cyclohexane
by volume of cyclohexane absorbed before measurement receiver measured after subtracting the volume of cyclohexane receiver Determination.
[0038] The average pore diameter of the catalyst (preferably measured according to DIN 66133) is preferably 5_20nm, more preferably 8_15nm. Particularly preferred are
the catalyst total pore volume (pore diameter greater than or equal to 3. 5nm and pore volume of air, measured in accordance with DIN66133 mercury porosimetry) of at
least 50%, preferably more than 70% fall within the diameter of 3. 5_50nm range holes (mesopores).
[0039] The average particle size (measured by sieving) to 10ym-10mm, preferably O. particularly preferred mean particle size of the catalyst in the process of the present
invention, 1_5_ preferably used. Preferably an average particle size of d5 (l is 2-4mm, particularly of the solid catalyst 3_4mm.
[0040] In the method of the present invention, the catalyst may be used in the form of molded bodies. The molded body may take various shapes. Preferably spherical,
extrudate or sheet molded in the form of the catalyst. Molded body having the above preferred average particle size.
[0041] The catalyst may also be applied to the carrier (e.g. metal, plastic, ceramic carrier), the reaction is preferably applied with respect to the catalyst to be applied in
the form on an inert carrier. In particular, the catalyst of the present invention may be coated on a metal support (e.g., a metal plate or a metal fabric). Such catalysts of
the present invention with a carrier, for example, can be used as an inlay in a reactor or column reactor of fear evaporated. The carrier may be metal balls, glass balls or
ceramic balls or ball inorganic oxide. If the catalyst of the present invention is coated on an inert support, then do not consider the quality and composition of the inert
carrier in the measurement of the catalyst composition. [0042] particularly preferably used in the form containing magnesia, alumina (Al2O3), and Ni catalyst, for
example, silicon oxide can be prepared by the following method, the method comprising the steps of:
[0043] Al) with an acidic aqueous solution of magnesium aluminosilicate, and
[0044] BI) calcining the treated aluminosilicate with an aqueous solution of a magnesium salt.
[0045] The aluminosilicate refers to a compound consisting essentially of alumina (Al2O3) and Ni silicon oxide (SiO2) in the form of composition share. However, the
aluminosilicate may contain a small amount of an alkali metal oxide or alkaline earth metal oxide. In this method, it may be used zeolites (such as zeolite A, X, Y, USY or
ZSM-5 zeolite or amorphous (e.g. MCM 41 from Mobil Oil)) as aluminosilicates. Aluminosilicates used in the process may be amorphous or crystalline. Suitable
commercially available aluminosilicate method of the present invention is used as starting material may be, for example, by precipitation, or gelation of the
aluminosilicate solution prepared by heat. In this method, preferably containing 5 to 40 mass%, preferably 10 to 35 mass% of alumina and 60-95% by mass, preferably 65-
90% by mass of Ni silicon oxide aluminosilicate (on dry basis materials, processing: burning at 850 ° C I h). The composition of the resulting catalyst or aluminosilicates
can be, for example, by classical analysis, by means of a melt of molten Borax and RFA (X-ray uorescence analysis), X-ray energy dispersive analysis, a ame
spectrophotometer (Al and Mg, non-Si), wet digestion and subsequent ICP-OES (inductively coupled plasma emission spectrometer) or be measured by atomic
absorption spectrometry. May be used in the present process is particularly preferred aluminosilicate terms of Al2O3 content of 13% by mass, the content of Ni in the
form of silicon oxide was 76 mass%. This baby move salt provided by GraceDavison company name Davicat O 701.
[0046] The aluminosilicates can be used in the process in different forms. Thus, the aluminosilicate can be used in the form of a molded body (e.g., tablets, pills, granules,
extrudates or strands). However aluminosilicates can also be used in the form of an aluminosilicate powder. From the powder may have different average particle sizes
and different particle size distribution as a starting material. Preferably, for producing molded bodies using 95% of the particles have a 5-100 μ m, aluminosilicate powder
is preferably 20-30 μ m and particularly preferably 10-30 μ m mean particle size. Particle size may be measured by, for example, by the company Malvern laser light
scattering particle analyzer (e.g. Mastersizer 2000).
[0047] To prepare a magnesium salt dissolved in water or an aqueous solution of the compound becomes soluble in water by the addition of an acid magnesium
compound. Preferably, as a nitrate salt. Preferably, a strong mineral acid containing a salt (e.g. magnesium nitrate hexahydrate or magnesium sulfate heptahydrate)
magnesium as magnesium salt solution. As used acidic alkali metal and / or alkaline earth metal salt aqueous solution preferably has a pH of less than 6, preferably less
than 6-3, and particularly preferably 5. 5-3. 5. The pH can be measured for example by means of a glass electrode or a test paper. If the salt solution has a pH of greater
than or equal to 6, then the pH by adding an acid, preferably present in alkali metal salt and / or alkaline earth metal salt of an acid in the solution is adjusted. Preferably,
when the alkali and / or alkaline earth metal salt solution contains nitrate as, using nitric acid as the acid. Magnesium content of the magnesium salt solution used is
preferably O. l-3Mol / l, preferably O. 5-2. 5Mol / l.
[0048] The processing in step Al) may be adapted in various ways so that the aluminosilicate into contact with the magnesium salt solution is performed. Approach is
possible with the magnesium salt solution, for example, dipping, soaking, spraying or pouring aluminosilicate. It may be advantageous, when treating aluminum silicate,
magnesium aluminosilicate solution O. acting on at least 1-5 hours, preferably 5-2 small O. inch. When the soaking treatment is performed by simple, this effect may be
especially advantageous in time.
[0049] In a preferred embodiment of the method step Al), the solution was treated with magnesium aluminosilicate, especially aluminosilicate molded body may be
suitable for this purpose, for example, by vacuum impregnation apparatus for vacuum impregnation. By this treatment, the aluminosilicate is rst evacuated in a vacuum
impregnation apparatus. Then, to draw the magnesium salt solution over the upper edge of the support bed, such that all of the aluminosilicate is covered with the
solution. In small preferably O. 1-10 inches, more preferably O. 5-2 hours after the duration of action is not absorbed by the support of the solution was discharged. [0050]
In the method of Step Al) ー a further preferred embodiment, with an alkali metal and / or alkaline earth metal aluminosilicate solution treatment, especially
aluminosilicate molded body, for example by spraying or irrigation silicoaluminophosphate salt is carried out. Preferably sprayed or irrigated with a magnesium
aluminosilicate solution, wherein the solution is sprayed or poured onto a rotating drum in the aluminosilicate. The process may be ー step, i.e., the entire amount of the
magnesium salt was added in one step to the aluminosilicate at the start. However, the salt solution may be metered in small portions by spraying or pouring, added time
is preferably 0.1 to 10 hours, and preferably 1-3 inches smaller. Preferably the amount of salt solution measured, so that all solution is absorbed aluminosilicate. In
particular, there are spray and immersion may be cast (e.g. cone mixer or intensive mixer, such as those provided by the Erich Company) Ester In the conventional device
in industry.
[0051] Step Al) was treated with magnesium aluminosilicate or may be performed in a plurality of sub-steps in the ho. In particular, the process may be performed in two
or more substeps. It can be the same in each of the magnesium salt solution in a single step by step, or by using a magnesium salt solutions of different concentrations
in the respective sub-step. For example the magnesium salt solution can be rst added to a portion only of aluminosilicate, optionally after intermediate drying, the
remainder being added for Surplus magnesium salt solution at the same or different temperatures. Step Al) not only carried out in two or more substeps. Likewise, the
method may have a plurality of step Al). In this case, the different steps Al) may also be used in terms of the concentration of the magnesium salt solution of the same or
different.
Process may [0052] Step Al) is preferably in 10_120 ° C, more preferably 10_90 ° C, particularly preferably 15_60 ° C and most particularly preferably carried out at a
temperature of 20-40 ° C.
[0053] It may be advantageous to add to or mixed to one or more additional Ji aluminosilicates or magnesium salt solution in step Al) in the. These additives may, for
example, binders, lubricants or a molding aid. Suitable adhesive may be, for example, boehmite or pseudo-boehmite, boehmite e.g. containing about 77% by mass of
Al2O3 under the name Disperal provided by SasolDeutschland GmbH. If the added boehmite, particularly Disperal as the binder, it is preferably added as a gel which can
be, for example, by an aqueous solution of the gel to 803 parts by mass of 28 mass% nitric acid was added with stirring I. 197 parts by mass Disperal, thoroughly stirred
for 3 hours at 60 ° C, cooled to room temperature and added water may be volatilized obtained. Silica may be used (Kieselsauer), in particular pyrogenic silica as a
molding aid, Degussa AG, for example those sold under the name AeiOsil, boehmite, clay, kaolin, kaolinite, ball clay and other particles skilled in the art for this purpose
commonly used materials. For example, graphite may be used as aids in better lubricant into a sheet.
[0054] or two or more of the above ー adding additives may be performed in various ways, in step Al) in the. In particular, the addition may be performed during the
treatment with the magnesium salt solution aluminosilicate. E.g. aluminosilicate, magnesium salt and the additive solution can be lled into ー Ester The equipment then
uniformly mixed. Another possibility ー dry mixed rst and aluminosilicate Ji added, then add the magnesium salt solution. Additives can be metered into a solution of
magnesium aluminosilicate and simultaneously in another variant of ー. Can be added, or by spraying several times in one pour. Addition time is preferably less than 5
hours, more preferably less than 3 inches. It may be advantageous, then mixing the mixture O. 1-10 hours, preferably O. 5-3 hours.
[0055] The preparation of the catalyst is preferably used with at least the method steps BI), calcined with alkali and / or alkaline earth metal aluminosilicate solution was
treated in process step BI) in. The calcination is preferably (e.g. in a gas stream from one or more of these constituents containing such as air, nitrogen, carbon dioxide,
and Ni / or one or more noble gases or gas ow) is in a ow. The calcination is preferably carried out in the case of using air as the gas stream.
[0056] The calcining step in the method BI) is preferred, more preferably at 300_800 ° C at a temperature of 200-1000 ° C. The calcination is preferably carried out O. 1-10
hours, more preferably 1-5 hours. Particularly preferably, the calcination is carried out O. 1-10 hours at 200-1000 ° C, preferably 300-800 ° C, preferably 1-5 hours.
[0057] The calcination is preferably carried out in industry Ester shaft furnace. Calcination can also be carried out in other known Ester The equipment (e.g., a uidized
bed calciner, a rotary tube furnace or disc furnace).
[0058] It may be advantageous, step Cl) between steps Al) and BI), dried over magnesium aluminosilicate solution was treated in this step. In the drying step Cl) may be
carried out at 100-140 ° c. Preferably, the drying is carried out in a gas stream. Dried in a gas ow such as, for example, it may contain air, nitrogen, carbon dioxide and /
or one or more noble gases or gas ow from one or more of the above-described constituents. By using the alkali metal and / or alkaline earth metal and the solution
treated intermediate drying step prior to calcination, the calcination can be achieved not release large amounts of water vapor. This evening Bu, can be avoided by drying
the catalyst was calcined shape emitted from water damage play.
[0059] depends on the desired catalyst should be present in what form, it may be advantageous by the additional method step of adapting prepared accordingly. If
desired, for example, a powdery catalyst prepared by this method, the aluminosilicate used in the aluminosilicate in powder form and, for example, treatment with the
magnesium salt solution cone mixer (e.g. by dipping), optionally dried and subsequent calcination. However, a powdery catalyst was prepared by the following method
may be, i.e. by milling and sieving the catalyst molded body was processed into a powdery catalyst.
[0060] The catalyst may be for example molded body strands, spheres, pellets or a sheet is present. For molding the catalyst (catalyst molded body), depending on the
respective molded variation, addition processing, dried, calcined Bu Xi method step, also additional process steps such as molding, milling or sieving. Urging molding aid
may be in the process of opening a different location. Preparation of the catalyst body may be molded in different ways:
[0061] In a rst variant embodiment, the catalyst moldings, in particular molded catalyst of the present invention can be obtained by the following manner, an aqueous
solution of magnesium aluminosilicate molded body that is treated with an acid, and optionally dried and then calcined.
[0062] In a second embodiment, the catalyst molded body can be obtained by the following manner, i.e., an aluminosilicate powder is rst treated with an acidic aqueous
magnesium salt solution, then dried and then calcined if necessary, and the resulting catalyst powder by conventional methods conventional in the art such as extrusion,
extrusion, pelleting, tableting, granulation or coating process into a catalyst molded bodies. Additives required for molding (e.g., adhesive or other additives) may be
prepared in various locations, such as adding in method step Al) in the. From the powder may have different average particle sizes and different particle size distributions
when the aluminosilicate powder as a starting material for the preparation of molded bodies. Preferably, for production of molded bodies using 95% of the particles have
a 5-100 μ m, 20-30 μ m is preferably 10-30 μ m and particularly preferably a particle size (measured by laser scattering method) aluminosilicate powder .
[0063] In a third embodiment of the method, the catalyst pellets can be obtained by a process, i.e., in the process step Al) with an acidic aqueous solution magnesium
aluminosilicate, optionally drying (method step CI)) and in the subsequent process step BI) is calcined, for example in an Eirich mixer and adding a binder in the case
where the resulting catalyst powder pelleting, drying the resulting pellets in a further method step Cl), and then in a further method step BI) it is calcining the resulting
pellets.
[0064] In a fourth embodiment of the production method, the catalyst pellets can be obtained by a method, i.e. a mixed aluminosilicate powder, a binder and an acidic
aqueous magnesium salt solution in process step Al), and for example an Eirich a mixer for aluminosilicate thus treated powder pelleting and drying the resulting wet
pellets and then calcined in a stream in the process of step Cl) in method step BI) in.
[0065] In a fth embodiment of the production method, the sheet can be obtained by way catalyst, i.e. a mixed aluminosilicate powder, a binder in the process of step Al),
the lubricant and optionally the acidic aqueous magnesium salt solution , for example in a Eirich mixer is thus treated aluminosilicate powder having an average diameter
pelleting preferred, more preferred and particularly preferred 1-3_ l_5mm (particle size can be measured by sieving is O. 5-10mm e.g. ) pellets, and drying the resulting wet
pellets and then optionally calcined in the air stream in the process of step Cl) in method step BI) in. Then, in the case of the method in step Al) are still not mixed with
lubricant, a lubricant may be incorporated (e.g., graphite) was added to the obtained pellets, and then on a commercially available tablet press (e.g. rotary press)
tabletting. In the case where the method steps are not carried out BI), the sheet can optionally be calcined or calcined after method step BI) in. [0066] In a sixth
embodiment of the production method, the sheet can be obtained by the catalyst method, a preform molded catalyst precursor can be obtained, for example, as soon
pellets in the third embodiment or fourth embodiment is ground and the resulting particles / powder was sieved to obtain catalyst particles can be tableted, a lubricant
and mixing these particles. Then thus prepared granules may be subjected to tableting. In the case where the method steps are not carried out BI), the sheet may be
subsequently calcined in method step BI) in. If in the preparation of the pellets (e.g., in the process step of Al)) have been added to the lubricant, the lubricant may be
omitted mixed.
Materials [0067] The coated catalyst can be prepared in a seventh embodiment of the method of the present invention / carrier. First, catalyst powder prepared in this
embodiment by a process, i.e., in method step Al) aluminosilicate powder treated with an acidic aqueous magnesium salt solution, optionally drying (method step CI))
and optionally calcining (Method step BI)). The catalyst powder thus obtained was then suspended into the suspending agents (e.g. water or alcohol), wherein the binder
can optionally be added to the suspension. The suspension thus prepared was then coated onto each may be any material. Drying (process step CI)) and subsequently
calcined (method step the BI)), optionally after coating. In this way a material with a preferred catalyst-coated preparation / carrier. The material / carrier may be, for
example, a metal plate or a metal mesh (e.g. they may be used as a reactor or column, notably the reaction was distilled inlay fear of the column), or metal balls, glass
balls or balls inorganic oxide.
[0068] In an eighth embodiment of the production method of the catalyst may be prepared as follows, in particular the catalyst of the present invention extrudates, i.e.,
aluminosilicates mixed in a kneader or Eirich mixer in the process of step Al) in powder, acidic alkali metal and / or alkaline earth metal salt aqueous solution, a binder
(e.g., Disperal) and other conventional additives for extrusion molding (e.g. clays such as boehmite or attapulgite), and extruded in an extruder having an average
diameter is preferably O. 5-10_, more preferably 1-5_ and particularly preferably extrudates 1-3_, the resulting wet extrusion step in the process was optionally Cl ) dried
and then calcined in the gas stream in the process of step BI) in.
[0069] Particularly preferably, MTBE decomposition at 200-400 ° C, preferably at a temperature of 230-350 ° C under these preferred catalyst (Mg / Al / Si mixed oxide)
situation.
[0070] In step a) the reaction pressure is preferably O. I-IOMPa (abs), and more preferably is O. 5-0. 8MPa (abs). Carried out at a WHSV (weight hourly space velocity) is
preferably decomposed in O. Ιϋ1, preferably Uh-1Gig MTBE per kg of catalyst per hour) of. MTBE is preferably a single pass conversion of 50 to 98%, more preferably 80 to
95%. Decomposition may (e.g., in a tubular reactor, a shell and tube reactor, a shaft furnace or a uidized bed reactor, or a combination thereof) are performed in a
conventional reactor.
[0071] Preferably, the decomposition in the gas phase in the reactor, the reactor is equipped with heating jacket and heated by the heat transfer uid, wherein the
decomposition temperature is lowered such that any position in the region of the catalyst / reaction zone to thermometer starting below 50 ° C, preferably below 40 ° C,
particularly preferably 1-30 ° C, the heat transfer medium in a reaction mixture in the sleeve and to the convection ow through the reactor, the reactor inlet heat transfer
between the reactor outlet and the position of the medium temperature difference is below 40 ° C. The maximum temperature drop by the plurality of parameters (e.g. by
the temperature of the heat transfer medium for heating and by heat transfer medium ow velocity through the sleeve) is adjusted.
[0072] Preferably, the inlet temperature, the gaseous starting materials, especially preferred embodiment of the present invention in the process of step a), more than 200
° C, preferably more than 230 ° C and particularly preferably more than 250 ° C. Inlet temperature of the starting material can be adjusted in a heater connected upstream
of the reactor. In the case of using a fresh catalyst when MTBE decomposition, especially fresh magnesium oxide / alumina / silica catalyst, the inlet temperature is
preferably 250 ° C _270 ° C. Advantageously during operation it is, as the degree of deactivation of the catalyst, in order to maintain stable conversion rate up to the inlet
temperature was raised to 400 ° C. Can not be maintained if the conversion rate reached 400 ° C, it is advantageous to fully or partially replace the catalyst.
[0073] The reactor, in the case of this preferred embodiment, especially in the process of the present invention step a) is preferably O. l-5h_ \ 1-31Γ1 particular space
velocity (weight hourly space velocity (WHSV), starting material in kilograms per kilogram of catalyst per hour count) single pass operation.
[0074] The reactor, when this particular preferred embodiment of the present invention in the process of step a), may be provided in each of an arbitrary spatial directions.
If the reactor has a reactor tube, the reactor tube then these may also be any direction in the space. However, this reactor is preferably in such a way that the tube reactor
or reactors vertical alignment. In a vertically oriented reactor, the heat transfer medium is preferably supplied to the uppermost position of the sleeve at or near the
highest position and the withdrawn position at the lowest position of the reactor at or near the lowest position or return position. The reaction mixture in the reaction
zone and the heating medium is preferably in the sleeve of ow through the reactor in the same direction. Particularly preferably, the reaction zone and the heat transfer
medium through the reactor the reaction mixture from the down ow reactor or the sleeve.
[0075] In order to achieve uniform heating of the reaction zone, it may be advantageous not only from a position, but a plurality of substantially identical height positions
to the heat transfer medium supplied to the reactor. In order to avoid when using a shell and tube reactor the intermediate tube relative to the edges of a larger
temperature drop in the tube, it may be advantageous in one or more inlet nozzles are provided for the heat carrier medium, which facilitates the heat nozzle an
intermediate transfer medium to the tube. Avoid temperature uctuations in the cross section of the envelope in this manner.
[0076] The heat transfer medium can be discharged from the reactor at one or more positions. If the heat transfer medium from the reactor and owed through, it can be
ensured by the structural measures in the reaction zone (e.g. a reaction tube) are all surrounded by the heat transfer medium. This may be provided by, for example, the
heat carrier uid stream fed to the reactor ba e member (Umlenksegment) or the guide plate realized.
[0077] outside of the reactor, heat transfer medium may be directly or indirectly heated to the desired temperature and pumped through the reactor.
[0078] The salt melts may be used, water or heat transfer oil as heat transfer medium. For the temperature range of 200-400 ° C using a hot oil it is advantageous,
because compared to other aspect requires lower investment by thermal cycling of hot oil. Hot oil can be used, for example, under the trade name Marlotherm (eg Sasol
Ole ns & Surfactants GmbH of MarlothermSH), Diphyl (Bayer Company)> Dowtherm (Dow Company) or Therminol (Therminol company) to sell those. These synthetic
heat transfer oil based preparation is substantially thermally stable cyclic hydrocarbons.
[0079] Preferably the temperature of the heat transfer medium owing in the reactor than the starting material had high 10-40 ° C, more preferably at a temperature of 10-
30 ° C is introduced into the heating jacket of the reactor. The temperature of the liquid heat transfer medium in the reactor on the difference, i.e., the inlet temperature of
the heat transfer medium on entering the heating casing and the heating medium leaving the heating jacket at a temperature difference between the outlet temperature
preferably below 40 ° C, in particular preferably below 30 ° C, particularly preferably 10-25 ° C. The temperature difference may be subjected to mass ow rate of the
heating sleeve (kilograms per hour) is adjusted by the heat transfer medium per unit time.
[0080] The method of the present invention, the step a) of the preferred embodiment may be carried out in all suitable reactor equipped with heating jacket and heated by
the liquid heat medium. Such a reactor containing a space wherein the reaction zone (catalyst zone) containing the catalyst was heated heat transfer medium circulation
tube separated. The method of the invention is preferably in a plate reactor, a tubular reactor, a plurality of parallel tubular reactors with each other or connecting a plate
reactor, or by a shell and tube reactor. The method of the invention is preferably carried out in a shell and tube reactor.
[0081] It should be noted that the presence of a catalyst wherein the hollow cavity need not only conventional semantics tube. The cavity may not have an annular cross-
section. It may, for example, a triangular or elliptical shape. [0082] The con guration of the reactor the material used, in particular, the reaction zone is separated from the
heating sleeve material preferably has a high thermal conductivity (greater than 40W / (m · K)). As a material of iron or iron alloy is preferably used having a high thermal
conductivity (e.g., steel).
[0083] If the method of the present invention is conducted in a shell and tube reactor, the tubes preferably having l-15m, and more preferably
And particularly preferably 3-9m length of 5-9m. In the method of the present invention, a shell and tube reactor used in each of the tubes preferably has a 10-60mm, and
the inner diameter is more preferably 20_40mm is particularly preferred 24_35mm. Each tube shell and tube reactor as used in the method of the present invention has 1-
4_, preferably 5-3mm I. wall thickness may be advantageous.
Shell and tube reactor is used [0084] In a preferred embodiment of the present invention is a process step a), the tubes preferably arranged parallel. The tubes are
preferably arranged uniformly. Tube may be provided, for example, square, triangular or rhomboid. Particularly preferred are set as follows, in which form an equilateral
triangle, i.e. with the same pitch tube midpoint actually connected to three adjacent tubes. In the preferred method of the present invention wherein each tube has
another 3-15mm, particularly preferably is a shell and tube reactor 4_7mm in pitch.
Conversion rate under conditions [0085] Preferably, in step a) is greater than the decomposition of MTBE conversion of 2_ methoxybutane. In this simple manner to
ensure that the concentration of decomposition products of linear butenes less than 1000 ppm by mass, based on the C4-ole n fraction, even in the overhead stream (II)
containing MTBE based on the count is higher than 1000 ppm by mass of 2 The same is true when methoxybutane (MSBE). The overhead stream (II) content contained
MSBE, may need to be adjusted to a condition, in which the conversion rate is signi cantly lower than MSBE MTBE conversion, i.e., for example, at least 50%. These
conditions can be determined by simple preliminary tests.
[0086] The main reaction steps in the process of the present invention, the method a) is decomposed into isobutylene and methanol MTBE. Conversion depends on the
set of MTBE, which has a decomposition product preferably 2-45 wt%, more preferably 3-25 mass% and the content of residual MTBE particularly preferably 5-15% by
mass. Decomposition products (II) methanol content is preferably 25-35% by mass, preferably 30-35% by mass. Decomposition products of isobutene content is
preferably 25-62 mass%. , Preferably 50-60% by mass. Is formed as a side reaction may occur diisobutylene from isobutylene and methanol to DME reaction. 2-
methoxybutane starting material supplied to the process step a), optionally containing portion may be decomposed into linear butenes, and tert-butanol contained (TBA)
is decomposed into isobutylene and water. Thus, the component decomposition product (II) produced by the reaction as another particular may comprise diisobutylene,
dimethyl ether, water and linear butenes.
[0087] Method step b)
[0088] To further workup decomposition product mixture, the decomposition product (II) is separated into an overhead stream (III) containing isobutylene and a bottoms
stream containing the unconverted MTBE (IV distillation step b)) . The method steps b), the decomposition product (II) is separated by distillation overhead stream (III)
containing isobutylene and a bottoms stream containing MTBE non-transformed (IV) is preferably at least one column, and more preferably only in a distillation column.
[0089] In process step b) preferably used in the distillation column preferably has 20-55, more preferably 25-45 and particularly preferably 30-40 theoretical plates.
Depending on the actual number of stages, the reactor e uent composition and the desired composition of the distillate and bottoms product purity, a re ux ratio of
preferably less than 5, more preferably less than I. The method may be preferred operating pressure in step b) the column was adjusted to O. 1-2. OMPaus). To save the
compressor, it may be advantageous, operation at a lower operating pressure than the column in process step a) R decomposition reactor pressure. In order to be able to
condense isobutene by means of cooling water, it requires a pressure of about 0.5MPa (abs) a. If the decomposition method of step a) is operated at a pressure of, for
example, 0.65MPa (abs), then it may be advantageous method step b) is carried out in a distillation column 0.55-0.6MPa (abs) operating pressure. In order to heat the
evaporator may be used such as steam of 0.4MPa. The bottom product (VI) preferably contains a non-transformed, MTBE, methanol and byproducts may contain (e.g.,
diisobutylene) and / or 2-methoxybutane. The overhead product III is preferably purity of greater than 95% by mass of isobutene, based on the total overhead product
weight. [0090] Optionally, the process step b) may be designed to perform at least one column of the reactive distillation column. This embodiment of the method of the
present invention has the following advantages, i.e. the entire process by the conversion of the MTBE process step a) is the untransformed portion of MTBE
decomposition reaction section is in process step b) a reactive distillation column isobutene and methanol to mention smell.
[0091] In the reaction section of the reactive distillation column can be used for all of the catalytic decomposition of MTBE as a homogeneous catalyst U. Preferably
using an acid as a catalyst. For acidic catalyst used in the reaction section of the reactive distillation column is especially preferred group is a solid acidic ion exchange
resins, particularly sulfonic acid group-containing solid acidic ion exchange resins. Suitable acidic ion exchange resin, for example, those prepared by sulfonation of
phenol / aldehyde condensates or oligomeric aromatic vinyl compound. Examples of the aromatic vinyl compound used to prepare the oligomers are styrene, vinyl
toluene, vinyl naphthalene, vinyl ethylbenzene, methyl styrene, vinyl chlorobenzene and vinyl xylene, and divinyl benzene . In particular the use of an oligomer prepared as
precursors having sulfonic acid groups ion-exchange resin obtained by the reaction of styrene and divinyl benzene. The resin may be in a gel, macroporous spongy shape
or prepared. Properties of such resins, in particular, porosity, stability, expansion or contraction exchange capacity and the speci c surface area can be varied by the
production process.
[0092] The ion exchange resin in the reaction portion of the reaction distillation column may be used in their H form. Styrene - divinylbenzene type strongly acidic resins
sold in particular under the trade names: DuoliteC20, Duolite C26, Amberlyst 15, Amberlyst 35, Amberlyst 46Λ AmberliteIR-120Λ Amberlite 200, Dowex 50, Lewatit
SPC118 ^ Lewatit SPC 108, Κ2611, Κ2621, OC 1501.
[0093] The pore volume of the ion exchange resin used is preferably O. 3-0. 9ml / g, especially O. 5-0. 9ml / g. Resin particle size is preferably O. 3mm-1. 5mm, more
preferably O. 5mm-1. 0mm. The particle size distribution can be chosen narrow or wide. Thus, for example, may be used having a very uniform particle size
(monodisperse resins) ion exchange resin. Capacity of the ion exchange resin is preferably O. 7-2. O eq / the I, especially I. 1-2. O eq / 1, based on the form provided by
the meter.
[0094] optionally in the method step b) is designed as a part of the reaction column of the reactive distillation column, the catalyst may be integrated into the ller Ij (e.g.
KataMax® (as described in EP 0,428,265), or KataPak® (EP 0396650 or e.g. the DE 29807007. 3U1)), the polymerized onto or molded body (e.g. in the US 5244929).
[0095] Preferably, the reactive distillation column with a purely distillative separation section above the catalyst packing. Preferably, the region above the catalyst packing
having 5-25, preferably 5-15 theoretical plates. In the separation zone below the catalyst preferably contains 5-35, preferably 5-25 theoretical plates. Feeding the reactive
distillation column may be above or below the catalyst zone, preferably above.
[0096] In the reactive distillation apparatus isobutene into MTBE and methanol preferably at 60_140 ° C, more preferably 80_130 ° C, a temperature region of the catalyst
temperature range of 90-110 ° C and particularly preferably in the presence (column; bottom temperature can be signi cantly higher) carried out.
[0097] The reaction pressure on the operating principle of the distillation column can be selected operating conditions are similar to the above-described embodiments
selected for a pure distillation column. In this way, the reactive distillation column operating pressure is preferably adjusted to O. l_1.2MPa (abs). To save the compressor,
it may be advantageous, in the column than the method step a) decomposition reactor R operating at a lower operating pressure operation. In order to be able to
condense isobutene by means of cooling water, it requires a pressure of about 0.5MPa (abs) a. If the decomposition method of step a) is operated at a pressure of, for
example, O. 65MPa (abs), then it may be advantageous method step b) is carried out in a distillation column 55-0. 6MPa (abs) operating pressure of O. . For example,
using heated vaporizer O. 4MPa of steam. [0098] The hydraulic loading in the catalytic packing of the column is preferably from 10% -110% of its over ow point of the
load, preferably 20% -70%. The hydraulic load in the distillation column refers to a homogeneous liquid load of the column cross-section ascending vapor stream and a
descending liquid stream. Upper limit load by the maximum load characterized vapor and re ux liquid, above which separation in re ux liquid is raised due to the action
of entraining vapor stream is reduced or blocked. The lower limit of the load characterization lowest load, since the value below which column (e.g. trays) irregular ow or
no-load operation is reduced or interrupted the separating action (Vauck / Miiller, ^ Grundoperationen chemischerVerfahrenstechnik ,,, p. 626, VEB DeutscherVerlag
irGrundstoffIndustrie).
[0099] Also preferably obtained containing unconverted MTBE and methanol, and optionally diisobutene and by-products, for example, 2-methoxybutane in the case of
process step b) the column is designed as a reactive distillation column the bottom product (IV). The bottom product is fed to process step c). The overhead product
preferably comprises a purity greater than 95% by mass of isobutene.
[0100] obtained in the process step b) and preferably greater than 95% by mass of isobutene overhead product (III) can be used directly as the product sold or further
puri ed.
[0101] Since the isobutylene and methanol form a minimum azeotrope, thus obtained in the method step b) the overhead product (III) in addition to the main product
containing methanol is also particularly isobutene. The top product (III) may contain, as other components, such as dimethyl ether and linear butenes (the I-butene, cis-2-
butene, 2-butene), and water, wherein the dimethyl ether for example, by condensation of methanol, and linear butenes can be produced, for example, by decomposition
of 2-methoxybutane. If MTBE faster than 2-methoxybutane decomposition catalyst in the process of step a), then the stream II ratio of linear butenes to isobutene fed to
the reactor may be less than in the portion (R) of the feed in the ratio of 2-methoxybutane of MTBE. I.e., may be adjusted to the desired quality in terms of straight-chain
butenes isobutene by MTBE conversion (single pass).
[0102] That portion of the dimethyl ether may optionally be in the process of step b) has been separated from the top product (III) in which the condenser on the
distillation column or reactive distillation column as part of the operation condenser. In this condenser, C4 fraction contained in the overhead stream may be condensed
and partially in gaseous dimethyl ether contained in the overhead product withdrawn formula (III).
[0103] In method step b) the content of linear butenes resulting overhead product (III), preferably less than 10,000 mass ppm, more preferably less than 5000 mass ppm,
inter alia preferably less than 1000 mass ppm, based on the C4 ole n fraction fear meter. Wherein fear overhead fraction (III) in the I- butene content is preferably less
than 5000 mass ppm, preferably less than 1000 mass ppm, based on the C4-ole n fraction. 2-butene content (2-butene and two kinds) is also preferably less than 5000
mass ppm, preferably less than 1000 mass ppm, based on C4 ole ns fear meter.
[0104] Method steps c) and d)
Bottoms stream (IV) [0105] Method step b) obtained contains most of the methanol generated during the decomposition process step a) is the untransformed MTBE and
MTBE. The bottoms product may optionally contain byproducts (e.g., diisobutene and / or 2-methoxybutane). Method step b) the bottom stream (IV), obtained in process
step c) is separated by distillation bottom stream containing methanol (V) and MTBE-containing overhead stream (VII) and a side stream (VI) . Distillative separation is
preferably carried out under such conditions as to obtain pure methanol as a bottom product (V), and most of MTBE to obtain side stream obtained in (VI) is preferably in
the overhead product (VII) greater than 50 %, more preferably greater than 80%, particularly preferably greater than 95% of the feed (IV) contained in the diisobutylene.
Also said by-product optionally contained in the starting material and the method step a) is the untransformed 2-methoxybutane emissions, thereby avoiding excessive
circulating concentrations of such components. The overhead product (VII) back to the process step a), in the process step d).
[0106] Table I below shows the pure substances MTBE, 2- methoxy butane, methanol, t-butanol and diisobutene a boiling point at O. IMPa (abs) a. For various isomers
exist diisobutylene mentioned in terms of an exemplary boiling 2,4,4_ -I- trimethyl pentene. It should be appreciated that the boiling point to MTBE, 2- methoxy butane,
methanol, t-butanol and diisobutylene order increases. However components MTBE, 2- methoxybutane diisobutylene and methanol form a minimum azeotrope
simultaneously. These azeotrope and the boiling point of the same composition are listed in Table I, wherein the azeotrope with the Property Method "UNIFAC-DMD" (sJ
Gmehling, J. Li and Μ · Schiller, Ind. Eng. Chem. Res. 32, (1993), pp. 178-193) aid program Aspen Plus (12. I version) is calculated. Under these boundary conditions,
MTBE methanol azeotrope is a system of low boilers and can be) used as the column top product obtained in the process to step c. Diisobutylene and methanol is
formed between the MTBE methanol and pure methanol azeotrope boiling azeotrope. It can thus be diisobutylene - methanol azeotrope was separated into the side
stream, making it possible to generate almost no diisobutylene overhead product and a bottom product in the column. Obtained as bottom product nearly pure methanol,
wherein the sole as a minor component (other than water are not listed in Table 3) containing t-butanol.
[0107] Table I: pure substances and methanol azeotrope boiling point at lMPa (abs); the azeotrope "UNIFAC-DMD" Property calculation method.
[0108]
[0109] In the method step c) is separated by distillation bottoms stream (IV) is preferably carried out in only one distillation column. In process step c) preferably used in
the distillation column preferably has 20-80 theoretical plates, preferably 30 to 70 theoretical plates, particularly preferably 40 to 60 theoretical plates. Side stream may be
withdrawn position of the column above the feed inlet or below. Preferably, the side stream withdrawn position of the column above the feed inlet, particularly preferably
at a position above the feed between 2-12 theoretical plates. MTBE target conversion depends on the actual number of plates and the method step a), the method step c)
is less than 10 column, preferably O. 5_5 may be advantageous to re ux ratio operation. In the process of the present invention, the operating pressure of the column in
step c) is preferably adjusted O. 05-lMPa (abs), and more preferably O. 1-0. 3MPa (abs). Column may be used for heating steam, for example, O. 4MPa. The operating
pressure selected, be condensed by means of cooling brine, cooling water or air.
[0110] The bottom product obtained in process step c) (V) preferably contains more than 98 mass%, more preferably more than 99% by mass of methanol. In the TBA
content of the bottom product is preferably 500 to 3,000 mass ppm, the water content is preferably O. 5-0.8 mass%. Whereby the methanol is such a high purity that it can
be used as the product sold or used in conventional industrial synthesis of (e.g., esteri cation or etheri cation). However, methanol can also be required to be further
concentrated in a higher purity, a further distillation step. [0111] The overhead product obtained in process step c), (VII), and preferably contains most of the methanol
contained MTBE, and optionally 2-methoxy butane in the feed stream (IV), and back into the the reaction section (R) of the. The distillation conditions and the column
pressure, MTBE content is preferably 65-88 mass%, more preferably 75-85% by mass. Methanol content is preferably 10 to 35%, more preferably 12-18%. 2-
methoxybutane content is preferably 1-5% by mass. The overhead product (VII) to the reaction part preferably at re ux (R) prior to mixing with the feed to MTBE MTBE
stream (I), and the mixture was used as feed stream in the method step a).
[0112] In the method step b) the resulting side stream (VI) preferably contains nearly all diisobutylene amount contained in the feed stream (IV),. In addition, depending
on operation mode of the column, the side stream may contain 10-40% by mass of the feed stream (IV) 2- methoxybutane contained. Because of the operating method
and catalysts used, 2-methoxybutane not decomposed in the reaction section (R), resulting in an undesirable 2-methoxybutane discharge side when no re ux stream in
the circuit enriched danger, which can be a side stream is simply avoided. Side stream (VI) can be thermally utilized, used as starting material or as a fuel synthesis
apparatus components.
[0113] Method step f) after treatment isobutene
[0114] Commercially available polyisobutylene quality is typically substantially free of methanol. Methanol can (e.g. by extraction) stream (III) obtained from the process
step b) are separated according to known methods. From the stream (III) extracted by means of water or methanol may, for example, an aqueous solution for example in
the extraction column as an extractant. Preferably extraction with water or aqueous solution is extracted column having 4-16 theoretical plates in the preferred. Preferably
the extractant relative to the stream to be extracted in countercurrent manner through the extraction column. Extraction is preferably at 15-50 ° C, more preferably 25-40 °
C temperature. For example, in the case of using an extraction column having more than 6 theoretical plates operating at O. 9MPa (abs) and a temperature of 40 ° C, to
obtain isobutene content of more than 99% by mass of isobutene water saturation.
[0115] obtained in the extraction methanol-containing aqueous extract may be separated by distillation of water and methanol. Water may be returned to the extraction
stage as the extraction agent. Methanol may be used in conventional industrial synthesis, for example esteri cation or etheri cation.
[0116] moist isobutene stream from the extraction column may be isolated by separation of water and optionally dimethyl ether in the distillation column and then further
processed into dried isobutene. As the bottom product thus obtained was dried isobutene. In the overhead condensing system, the phase separation can be withdrawn
after liquid water and gaseous dimethyl ether. A distillation column for drying is preferably employed preferably has 30-80 theoretical plates, more preferably 40-65
theoretical plates. Depending on the actual number of trays and the required purity isobutene, re ux ratio is preferably less than 60, more preferably less than 40. Used for
drying the distillation column operating pressure is preferably adjusted to O. 1-2. 0MPa (abs) ο
[0117] described in detail in DE 10238370, for example, by extractive distillation, and isobutene. Containing overhead stream (III) is preferably isobutene in process step f
obtained from process step b)) was isolated by extraction from methanol and dimethyl ether and water separated by distillation and extraction of isobutylene.
[0118] methacrylic composition thus obtained may have, for example, are listed in Table 2:
[0119] Table 2: composition generally commercially available isobutylene [0120]
[0121] However, depending on purity, a lower concentration of the minor component if necessary are also envisioned.
[0122] isobutene prepared by the process of the present invention may be used, for example, the preparation of methallyl chloride, methallyl sulfonate, methacrylic acid or
methyl methacrylate. May be particularly advantageous may be separated methanol may be separated from the isobutylene, methanol and isobutene can be used for the
preparation of methyl methacrylate from the decomposition products. This method for preparing methyl methacrylate, for example, described in EP 1254887, which is
expressly incorporated herein by reference.
[0123] starting material
[0124] MTBE may use different quality as stream (I) containing MTBE in process step a). The mixture may be used such as pure MTBE, MTBE and methanol as MTBE-
containing stream ⑴, MTBE or a mixture of various industrial quality industrial MTBE and methanol. MTBE may be used in particular, or mixtures of different quality
industrial industrial MTBE and methanol as stream (I). Industrial MTBE (fuel quality), especially due to economic factors is the preferred raw material. Table 3 shows an
exemplary composition of the technical grade MTBE is usually OXENO Ole nchemie GmbH of.
[0125] TABLE 3 = Oxeno technical grade MTBE (fuel quality) is generally composed of
[0126]
[0127] Industrial MTBE may be possible according to known methods by reacting a mixture of C4 hydrocarbons removed therefrom polyunsaturated hydrocarbons (e.g.
ra nate I or the C4 distillate was hydrogenated) prepared in the reaction with methanol. The method of preparation of MTBE are described, for example in DE 10102062.
[0128] In the process of the invention may be particularly advantageous to use completely or partially by an optional method step e) separating the stream containing the
low-boiling MTBE was obtained from an MTBE-containing stream Ia as stream (I).
[0129] When MTBE-containing stream Ia comprising e.g. C4 and / or C5 hydrocarbons, the separated light boilers may be particularly advantageous. Preferably,)
separated in an optional process step e from Ia stream out low boilers (e.g., C4 hydrocarbons, and / or (: 5 hydrocarbon) may be performed in a distillation column the
distillation column is preferably so doing, as to enable. the overhead product was separated low boilers.
[0130] Method step e) preferably having 30-75 theoretical plates, more preferably 40_65 theoretical plates, distillation column particularly preferably 40-55 theoretical
plates is carried out. Depending on the actual number of stages, the desired composition and purity of C4 and C5 hydrocarbons with MTBE, the column is preferably 150-
350, especially 200-300 re ux ratio. In the optional method step e) the column is preferably O. 2-0. 6MPa (abs), preferably O. 3-0. 4MPa (abs) operating pressure
operation. For example, the heating tower can be used
O. 4MPa of steam. Depending on the selected operating pressure, it can be condensed by cooling with brine, cooling water or air. The overhead vapor can condense all or
only partially, such that the overhead product VIII may be withdrawn in liquid or vapor state. The overhead product VIII can be used as synthesized or thermal means.
[0131] If, for example, 2 to K1, K2 and K3 FIG column labeled I, or in the case of FIG process of the invention, these columns may be provided with inlays such as trays,
rotating inset, irregular bed and / or random packing.
[0132] For example consider the following type of trays used:
[0133] trays having holes or slots in the tray plate.
[0134] having a blister, covering or shield covering the short tube or chimney trays.
[0135] covered trays having holes in the active valve trays.
[0136] tray having a speci c structure.
[0137] In the rotary column having inlay re uxed for example, by spraying or spreading the rotary hopper to the heating walls as a lm by means of a rotor.
[0138] As described above, in the method of the present invention may be used with various irregular packing bed column. Such llers may consist of almost all
materials, in particular steel, stainless steel, copper, carbon, stoneware, porcelain, glass or plastic, and may have various shapes, in particular spherical, having a smooth
or pro led surface of the ring, having internal stent or the opening of the wall by an annular, wire mesh, and spiral saddle.
[0139] having a regular / neat appearance, for example, llers may be composed by a plate or a mesh. Examples of such llers is Sulzer Gewebepackung ΒΧ prepared
from metal or plastic, Sulzer LamellenpackungenMellapak made from sheet metal, Sulzer high conductive ller (e.g. MellapakPlus), of Sulzer structured packing
(Opti ow), Montz (BSH) and Kiihni ( Rombopak).
BRIEF DESCRIPTION
[0140] Figure I illustrates a block diagram of one embodiment of the apparatus may be a method wherein the present invention.
[0141] FIG. 2 shows a block diagram of another embodiment of the apparatus may be implemented in which the method of the present invention.
detailed description
[0142] The present invention 2 below described in more detail by means of FIGS. I and, but not to limit the invention in this exemplary embodiment described herein.
[0143] illustrates a block diagram of one embodiment of apparatus according to the invention may be a method in which I, in FIG. Feed stream (I) and the MTBE-
containing mixture at re ux stream (VII) and process step a) in a reactor (R) in the vast majority of the isobutylene and methanol decomposition. Decomposition products
(II) obtained in the reactor R in process step a) is fractionated in process step b) in the column as a mixture containing Kl isobutylene (III) and a bottom product (IV),
wherein the isobutene-containing mixture (III) may contain a small amount of methanol and dimethyl ether may contain, and the bottom product (IV) contains
unconverted MTBE, methanol and minor components generated during the decomposition of a major amount. The bottom product (IV) from process step b) is separated
in the process step c) the bottom product of column K2 (V), a side stream (VI) and an overhead product (VII). The bottom product preferably contains more than 98%
methanol. As the side stream (VI) discharging diisobutene and 2-methoxy butane (if present). The overhead product (VII) is returned to the reactor R. Kl column can
optionally be designed as a reactive distillation column. Optionally, a stream (I) and (VII) may be introduced separately or together in the reactor R. [0144] describes a
block diagram of another embodiment of the apparatus of the present invention may be implemented in which the method in FIG. FIG embodiment of FIG. 2 distinction I
embodiment in that the feed MTBE (Ia) is separated into an overhead stream (VIII) comprising low boilers (e.g., C4 and C5 hydrocarbons) in the pre-removal column K3,
containing MTBE is a stream of low boilers ⑴ as the bottom product, and then the stream separately or mixed with the re ux stream (VII) introduced into the reactor R.
[0145] The following examples serve to illustrate the present invention without limiting its scope of application, the application range of the speci cation or the claims is
given.
[0146] Example
Producing aluminosilicate molded body: [0147] Example a
[0148] First, 500g salt trick baby powder (manufacturer: Grace Davison, type: DavicatO 701, Al2O3 form content: 13 mass%, SiO2 content -J6 form mass%, Na2O content
of the form: 0 mass% I, in loss on ignition 850 ° C: about 11%), 363g Disperal gel (Al2O3 form content: 15.6%) and 370g deionized water (VE water) in an Eirich intensive
mixer companies uniformly mixed with each other, wherein said coagulation Disperal adhesive prepared by the following method: the 197g Disperal (i.e., Al2O3, content
of 77% by mass of boehmite from Sasol Deutschland GmbH) were stirred into I. 803g of nitric acid aqueous solution of 28% by mass, then in a covered container stir at
60 ° C 3 hours to form a gel and is continuously cut to maintain the uidized state, the gel was cooled to room temperature and supplemented with water may be
volatilized obtained. Followed by pelleting in an Eirich mixer's strength, to give a uniform circular pellet having a diameter of about l-3mm in 30-40 minutes. First, wet
pellets 120 ° C for and then dried at 2K / min in an air stream heated to 550 ° C, and calcined in an air stream 10h at this temperature. The aluminosilicate form of pellets
thus prepared contained 76% by mass of Al2O3 and 24% by mass of Si02. In addition, the catalyst prepared contained O. 12% by mass of sodium compounds (calculated
as sodium oxide). Sodium aluminosilicate composition derived from the amount and composition of the starting material is calculated. The aluminosilicate having a
porosity I. 15ml / g measured using the method described above epoxy hexane.
[0149] Example b: Preparation of shaped catalyst (according to the invention)
[0150] VE water from the magnesium nitrate hexahydrate and the impregnation solution containing a magnesium content of 4.7 mass% was prepared. PH of this solution
is 5. I. The screened portion of the aluminosilicate carrier prepared in Example I (diameter:.. 1 Omm-2 8mm) by vacuum impregnation method with an acidic solution of
magnesium nitrate impregnated. To this end, the pellet into glass tubes and the glass tube was evacuated for 30 minutes (water-jet pump the vacuum of about 25hPa).
Then extracted from below until the impregnation solution over a solid bed edge. In effect the discharge is not absorbed by the support was approximately 15 minutes.
First, in an air stream at 140 ° C wet pellets dried to a constant weight, and then at 3K / min was heated to 450 ° C and calcined at this temperature for 12h. The catalyst
prepared by the form of 68% by weight of silica, 21 mass% of alumina and 11% by mass of magnesium oxide. Further, the prepared catalyst further contains O. 11% by
mass of sodium compounds (calculated as sodium oxide). The calculated composition of the catalyst solution derived from the crushed material and the amount of
starting composition and leaching discharged. Example I The sodium content of silicon is used in the embodiment of aluminosilicate component. Pore volume
I. lml / g, measured by the above method cyclohexyl burn. [0151] The following calculation example performed by means of a steady state simulation program ASPEN
Plus (AspenTech company 12. I Edition). In order to obtain unambiguous data can be reproduced, using only commonly available data. In addition, all variations are to
abandon using reactive distillation. This simpli ed manner by those skilled in the art that can easily perform this calculation. Although the method is not used with
su cient accuracy for industrial equipment design, but to obtain the correct qualitative differences between means. In all the variant illustrated, MTBE can be what
conversion is improved by using reactive distillation.
[0152] In this embodiment, the use of T Property Method "UNIFAC-DMD" (s. J. Gmehling, J. Li, and M. Schiller, Ind. Eng. Chem. Res. 32, (1993), section 178-193 page). R
are modeled for a reactor of 1100 liter reactor volume is lled with a catalyst which assumes the form of magnesium oxide, aluminum oxide and silicon oxide, the
preparation of the catalyst described in Example a and b.
[0153] To the reactor was modeled using a reaction kinetic model based on experimental data by using a large amount of the catalyst in the calculation. Thus, in these
embodiments also include a putative reactor modeling the reaction temperature. Since both lists the composition of the stream entering the exhaust stream and reaction
stages, one skilled in the art can duplicate reactor having a predetermined conversion calculation example was repeated without knowing the precise dynamic
equilibrium.
[0154] Example I
[0155] Example I corresponds to the variant illustrated in FIG. I. According to Figure 1, it is assumed 1000kg / h having a composition listed in Table 4 in MTBE stream
(the I) (MTBE feed) is supplied as a feed apparatus MTBE decomposition. Since it is assumed linear butenes this embodiment, a higher concentration of saturated
hydrocarbons and C5 C4 hydrocarbon does not interfere with isobutylene in the product, it is possible to cancel the tower shown in FIG. 2 and K3 operate at higher
conversions the reactor.
[0156] Table 4: MTBE decomposition apparatus of Example I assumed the MTBE feed stream composition
[0157]
[0158] ⑴ and re uxed MTBE feed stream (VII) is mixed stream fed to the MTBE reactor R as the feed. Re ux stream (VII) refers to K2 column distillate stream, which
contains most of MTBE in the reaction section (R) in the untransformed, 2-methoxybutane and methanol. Composition virtual re ux stream (VII) and the mixture obtained
is supplied to the reactor feed stream R are given in Table 5.
[0159] reactor feed ((the I) a mixture, and (VII)) is in a liquid state compressed to the reaction pressure, heated and vaporized and a gaseous state at the temperature of
the reaction temperature corresponding to the reactor is supplied to the reactor (R) . The reactor was operated at 290 ° C and O. 82MPa (abs). Under these reaction
conditions the conversion was about 90% MTBE, 2-methoxy butane conversion was about 20%. The reactor e uent composition (II) is also given in Table 5.
Composition re ux stream (VII), the feed stream fed to the reactor and the reactor e uent R (II) is: [0160] TABLE 5
[0161]
[0162] The reactor e uent (II) may be partially condensed or fed to the column in two phases Kl. The column has 50 theoretical plates and a re ux ratio of 85 and O.
operated at O. 62MPa (abs) pressure. Material is added on top of the rst, counting from the top plate 38 for. Top temperature of 49.5 ° C, the bottom temperature is
113.7 ° C. The overhead product (III) is isobutylene purity of greater than 95% by mass of isobutene. Composition of the overhead product (III) is given in Table 6. Since
no pre-column K3 feed prior separation and C4 hydrocarbons from C5 hydrocarbons and MTBE 2- methoxybutane decomposition in the decomposition reaction, about
3000 ppm by mass of linear butenes content is relatively high, but always lower to 5000 mass ppm. Thus, isobutene product can be used in many industrial synthesis,
wherein the concentration of such interference can not afford to linear butenes. It can be removed to remove the methanol, dimethyl ether and residual water by
distillation followed by extraction with water if necessary.
[0163] Table 6: Example I Kl column distillate stream composition (III) and a bottoms stream (IV),
[0164]
[0165] Kl column bottom product (IV) comprising mainly unconverted MTBE (approximately 23% by mass) and methanol (about 75 mass%). Further particular containing
2-methoxybutane untransformed, t-butanol, and water generated by the reaction as well as from the feed of the MTBE diisobutylene. This stream is fed to the column Κ2.
[0166] Κ2 column having 55 theoretical plates and a re ux ratio of 3.2 and an operation in at O. 15MPa (abs) pressure. Material is added on top of the rst, counting from
the top plate 35 for. A liquid side stream from the upper imposed on the number of trays 26 extracted. Top temperature of 61. 8 ° C, the bottom temperature of 75. 1 ° C.
The bottom product composition (V) and a side stream (VI) listed in Table 7, the composition of the distillate column K2 (VII) are listed in Table 5.
[0167] Table 7: Composition of column bottom stream K2 (V) and a side stream (VI),
[0168]
[0169] containing most of the small amount of methanol was distilled off in the feed stream (IV) and the MTBE contained in a 2-methoxybutane column overhead
product. Wherein the use of such components and methanol form an azeotrope. Further may be all low boilers (DME, butene and pentane) was separated overhead.
Distillate (VII) is returned to the reaction section.
[0170] side stream (VI) containing all diisobutylene, further comprising ΜΤΒΕ, methanol, and trace-methoxybutane 2_ pentane. 2-methoxybutane through the discharge
may be such that these components do not reach undesirable concentrations in the circuit.
[0171] purity of more than 99% by mass and no diisobutylene Laid pure methanol as a bottom product (V). As only a minor component comprising TBA and water.
Accordingly, the bottoms stream (V) may be used on behalf of selling products and conventional industrial synthesis (e.g. esteri cation and etheri cation). However, if
desired, also possible to remove the methanol and water and concentrated to a TBA higher purity In a further distillation step.
[0172] Example 2
[0173] Example 2 corresponds to the separation of C4 / C5 hydrocarbons in the variant illustrated in column 2 of FIG Κ3. According to FIG. 2, it is assumed that 1000kg /
h of MTBE stream having (Ia) having the following composition is supplied as a feed to the MTBE decomposition apparatus, the composition of the feed stream with
respect to (I) of the Example I composition remains unchanged and it can be learned in table 4.
[0174] In the rst separation column K3 from MTBE stream (Ia) the C4 and C5 hydrocarbons until the residual hydrocarbons in an amount of 500 ppm by mass in
Example 2. The column has 50 theoretical plates and a re ux ratio of 211 and an operation in at O. 5MPa (abs) pressure. Material is added from above the upper tray 20
counting from the rst. Top temperature was 63. (TC, the bottom temperature is 111. 8 ° C. The column distillate (VIII) having a 10% by mass of residual amount of MTBE
can be further reduced by increasing the re ux ratio and / or number of plates separated MTBE content. table 8 shows the distillate stream (VIII) and MTBE stream
composition (I) as the bottoms stream of column K3 obtained.
Composition Example distillate stream (VIII) and a bottoms stream of column K3 2: [0175] TABLE 8
[0176]
[0177] possible to make free of low boilers Κ3 column bottom product (I) of the return stream (VII) are mixed, wherein the re ux stream (VII) refers to column Κ2 distillate
stream, which ΜΤΒΕ distillate stream containing most of the reaction section (R) non-transformed, methanol and 2-methoxybutane. Composition Example re ux stream
(VII) and obtained by mixing the reactor feed 2 are given in Table 9.
[0178] a mixture of MTBE stream (I) and a re ux stream (VIII) in liquid compressed to the reaction pressure, heated and vaporized and gaseous state is supplied to the
reactor (R) at a temperature corresponding to the reaction temperature in the reactor at in. The reactor was operated at 280 ° C and O. 8MPa (abs). Under these reaction
conditions the conversion was about 80% MTBE, 2-methoxy butane conversion was about 13%. The reactor e uent composition (II) is given in Table 9.
[0179] Table 9: Example 2 of the re ux stream (VII), reactor feed (Ia) and the reactor composition (II) of the discharge
[0180]
[0181] The reactor e uent is partially condensed product (II) or a two-phase fed to the column in Κ2. Kl plate number of the column, material feed position and operating
pressure constant with respect to Example I. O. The column is operated at a re ux ratio of 95. Top temperature of 49.5 ° C, bottom temperature of 112. (TC. As an
overhead product (III) obtained isobutene purity higher than 95% by mass of isobutene composition of the overhead product (III) can be known from the table 10.
because MTBE is separated from the C4 hydrocarbon feed, and (at the front column K3: 5 hydrocarbons discharged with the side stream and a 2-methoxybutane portion
with respect to the reaction in Example I from the circulation in more column K2 2-methoxybutane low conversion rate, with respect to the content of linear butenes in
Example I signi cantly decreased from about 940 mass ppm. thus, this embodiment of linear butenes isobutene content is less than speci cations of the commercial
embodiment 1000 ppm by mass required maximum limit (see Table 2). methanol removed by extraction with water if necessary, the residual water and separating
dimethyl ether followed by distillation.
MTBE (approximately 37 mass%), and methanol (about 61% by mass) [0182] Kl column bottom product (IV) contains most of the unconverted. Further particular
containing 2-methoxybutane untransformed, t-butanol, and water from the reaction as well as from the feed MTBE diisobutylene. This stream is fed to the column K2.
[0183] Table 10: Example Kl 2 of the column distillate stream composition (III) and a bottoms stream (IV),
[0184]
[0185] Κ2 column number of plates, the feed position, the side stream discharge position, operating pressure and re ux for Example I with the same ratio. The overhead
temperature was 62. I ° C, the bottom temperature was 75. (TC. Composition bottom product (V) and a side stream (VI) are shown in Table 11, column K2 distillate /
re ux stream (VII ) of the composition listed in table 9.
[0186] Table 11: K2 column bottoms stream (V) Example 2 Composition of the side stream and
[0187]
[0188] In the distillation column overhead product most of the feed stream MTBE (IV) and contained 2_-methoxybutane with a small amount of methanol. Wherein the
components utilized and methanol form an azeotrope. Furthermore all low boilers separated (DME, butenes and pentanes) overhead product. Distillate (VII) is returned to
the reaction section.
[0189] side stream (VI) containing all diisobutylene, further comprising of MTBE, methanol and 2_ methoxybutane. 2_ methoxybutane by discharging cycle may be such
that these components do not reach undesirable concentration. [0190] purity of more than 99% by mass and no diisobutylene Laid pure methanol as a bottom product
(V). As only a minor component comprising TBA and water. Accordingly, the bottoms stream (V) represents the sale of the product and may be used in conventional
industrial synthesis (e.g., esteri cation or etheri cation). However, if desired, methanol can in a further distillation step to remove water and TBA, and concentrated to a
higher purity.
Patent Citations (8)
Publication number Priority date Publication date Assignee Title
GB2096604A 1981-04-10 1982-10-20 Snam Progetti Decomposition of alkyl tert- alkyl ethers
Family To Family Citations
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US4727216A * 1983-09-12 1988-02-23 Chevron Research Company Dehydrogenation of isobutane over a zeolitic catalyst
FR2660651B1 * 1990-04-09 1994-02-11 Institut Francais Petrole Method for obtaining at least one tertiary ole n by decomposition of the
corresponding ether.
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ツ・インク
JP4649783B2 * 2001-06-21 2011-03-16 住友化学株式会社 The method of producing isobutylene and methanol
DE10231051A1 2002-07-10 2004-01-22 Oxeno Ole nchemie Gmbh A process for the preparation of high purity methyl tertiary butyl ether
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Cited By (18)
Publication number Priority date Publication date Assignee Title
Family To Family Citations
DE102005062699A1 * 2005-12-28 2007-09-06 Oxeno Ole nchemie Process for ne puri cation of 1-butene containing streams
Gmbh
DE102006040432A1 * 2006-08-29 2008-03-20 Oxeno Ole nchemie Catalyst and process for the production of isoole ns
Gmbh
WO2009021736A1 * 2007-08-14 2009-02-19 Saipem S.P.A. Modi ed tubular reactor and process for effecting catalytic reactions involving
thermal exchanges in which it is used
US8067655B2 * 2008-05-29 2011-11-29 Lyondell Chemical Diisobutylene process

Technology, L.P.
DE102008040511A1 2008-07-17 2010-01-21 Evonik Oxeno Gmbh A process for the preparation of isobutene by cleavage of MTBE-containing mixtures
EP2358637A1 * 2008-12-17 2011-08-24 Evonik Degussa Process for preparing an aluminium oxide powder having a high alpha-al2o3 content
GmbH
DE102009027404A1 2009-07-01 2011-01-05 Evonik Oxeno Gmbh Preparing isobutene by cleavage of MTBE
DE102009027405A1 2009-07-01 2011-01-05 Evonik Oxeno Gmbh A process for the regeneration of a catalyst
WO2011019465A3 * 2009-08-13 2011-04-07 Catalytic Distillation Integrated biodiesel production process

Technologies
DE102009029284A1 2009-09-08 2011-03-10 Evonik Oxeno Gmbh A process for the oligomerization of ole ns
DE102010030990A1 2010-07-06 2012-01-12 Evonik Oxeno Gmbh A process for the selective hydrogenation of polyunsaturated hydrocarbons in ole n-
containing hydrocarbon mixtures
DE102010042774A1 2010-10-21 2012-04-26 Evonik Oxeno Gmbh A process for the puri cation of MTBE-containing mixtures and for the preparation of
isobutene by cleavage of MTBE-containing mixtures
EP2500090B1 2011-03-16 2016-07-13 Evonik Degussa Silicon-aluminium mixed oxide powder

GmbH
DE102011005608A1 2011-03-16 2012-09-20 Evonik Oxeno Gmbh Mixed oxide compositions and methods for the production of isoole ns
US9067860B2 * 2011-10-17 2015-06-30 Shell Oil Company Process for converting an alkyl tert-alkyl ether into an alkanol and an iso-alkane
DE102012215757A1 2012-09-05 2014-03-06 Evonik Industries Ag A process for the preparation of linear butenes from methanol
CN103242119A * 2013-05-23 2013-08-14 南京工业大学 Method for separating mixture of diisobutylene and tertiary butanol
CN106378180A * 2016-10-28 2017-02-08 姚光纯 Method for preparing catalyst by steeping active component into target material in
targeting manner
* Cited by examiner, † Cited by third party, ‡ Family to family citation
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CN101134700B - Method For The Decomposition of Methyl Tertiary-Butyl Ether - Google Patents

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11/9/2018 CN101134700B - Method for the decomposition of methyl tertiary-butyl ether - Google Patents

Method for the decomposition of methyl tertiary-butyl ether

Original Assignee: 赢创奥克森诺有限责任公司

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2008-03-05 CN101134700A Application

2012-08-08 CN101134700B Grant

Info: Patent citations (8), Cited by (18), Legal events, Similar

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Claims (8) translated from Chinese

Description translated from Chinese

The method of decomposition of methyl tertiary butyl ether

[0009] Various methods known in the preparation of isobutene by MTBE decomposition.

[0023] d) the overhead stream VII returned to step a)

[0030] d) the overhead stream VII returned to step a).

[0031] Method step a)

[0043] Al) with an acidic aqueous solution of magnesium aluminosilicate, and

[0087] Method step b)

[0104] Method steps c) and d)

[0113] Method step f) after treatment isobutene

[0119] Table 2: composition generally commercially available isobutylene [0120]

[0123] starting material

[0132] For example consider the following type of trays used:

[0133] trays having holes or slots in the tray plate.

[0135] covered trays having holes in the active valve trays.

[0136] tray having a speci c structure.

Producing aluminosilicate molded body: [0147] Example a

[0149] Example b: Preparation of shaped catalyst (according to the invention)

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