CN1493552A - Method of producing isobutene joint producing dimetylether and dipolyisobutene - Google Patents
Method of producing isobutene joint producing dimetylether and dipolyisobutene Download PDFInfo
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Abstract
A process for preparing isobutylene along with dimethylether and dipolyisobutylene includes cracking reaction of methyl tert-butyl ether (MTBE) in the reactor containing solid acid catalyst at 230-270 deg.c, dewatering part of resultant methanol to obtain dimethylether, and further polymerizing part of isobutylene to obtain dipolyisobutylene.
Description
Technical Field
The invention relates to a method for producing isobutene and coproducing dimethyl ether and diisobutylene (also called diisobutylene), in particular to a method for preparing isobutene and coproducing dimethyl ether and diisobutylene by cracking methyl tert-butyl ether (MTBE).
Background
Isobutene is an important raw material for fine chemical engineering, and is also an important intermediate raw material or monomer for synthetic rubber and synthetic resin. Diisobutylene is an intermediate product of a detergent and is an important raw material for producing various chemical and fine chemical products such as octyl phenol, octyl amine, octyl diphenylamine and the like. Dimethyl ether is also an important chemical raw material, is widely applied to the industries of pesticides, medicines, dyes and daily chemical industry, is an aerosol propellant and a refrigerant with excellent performance, is an ideal substitute of chlorofluorocarbon which has destructive effect on the atmosphere, can be used as a propellant, has physical properties similar to liquefied petroleum gas, and can replace the liquefied petroleum gas as a civil clean fuel.
The production process for preparing the isobutene by MTBE cracking is a more process for preparing the isobutene in recent years, and has the advantages of simple production process, strong independence, rich raw materials, mild operation conditions, no special requirements on equipment and materials and small environmental pollution. Heretofore, suitable catalysts for the production of isobutylene by MTBE cleavage include cation exchange resins, silica-alumina, supported inorganic acid salts, solid phosphoric acid catalysts, acidic molecular sieves, niobic and tantalic acid and like acidic catalysts.
The reaction process of the process is as follows:
main reaction:
side reaction:
2 methanol (MeOH) → dimethyl ether (DME) + Water
tert-Butanol (TBA) → Isobutene (IB) + Water
2 Isobutene (IB) → Diisobutylene (DIB)
The main reaction generates isobutene and methanol, the methanol generated in the reaction can be further dehydrated to generate dimethyl ether and water, and the isobutene obtained in the reaction can be further reacted to obtain diisobutylene. At present, the production of high purity isobutene disclosed in the patent literature is mainly controlled by selecting an appropriate catalyst and controlling the reaction conditions, so that the contents of dimethyl alcohol and diisobutylene in the product are smaller and better, for example, in the method for producing high purity isobutene disclosed in US 6,072,095, the MTBE conversion rate is about 90%, the dimethyl ether content in the ether cleavage reaction liquid is about 0.5%, and the diisobutylene content is about 1.1%.
Dimethyl ether is an intermediate of useful chemical raw materials and organic raw materials, and the preparation method mainly comprises the following steps: dehydrating methanol by concentrated sulfuric acid or solid acid to prepare dimethyl ether; the synthesis gas is catalyzed by a solid catalyst to generate dimethyl ether, and the like, if a set of dimethyl ether production device is newly built, the investment cost is relatively high, and the investment conditions of the production device are differentaccording to different raw materials, generally, the synthesis gas is used as the raw material, the total investment of a 5000 ton/year dimethyl ether production device is about 1000 ten thousand yuan, and the total investment of a device for producing dimethyl ether by using methanol as the raw material on the same scale is about 700 thousand yuan.
The production method of diisobutylene is mainly sulfuric acid extraction, pure isobutylene polymerization and mixed C-C selective polymerization, and the former two methods have the problem of sulfuric acid corrosion, and the mixed C-C selective polymerization has no corrosion, but the product purity of diisobutylene is not high. U.S. Pat. No. 4,4,447,668 discloses a process for the production of high purity isobutylene with the co-production of diisobutylene, which comprises: after the reacted material at the outlet of the ether cracking reactor is used for extracting methanol by water, one part of the reacted material enters an MTBE fractionating tower to separate unreacted MTBE from isobutene and light components, the other part of the reacted material enters a dimerization reactor, the material at the outlet of the reactor contains diisobutylene and unreacted MTBE and is sent back to an MTBE refining tower arranged in front of the etherification reactor, and a diisobutylene product is obtained at the bottom of the MTBE refining tower. Although the method can simultaneously obtain isobutene and diisobutylene products, the method correspondingly increases equipment cost and operation cost due to the addition of a dimerization reactor.
If a dimerization reactor is not added in a production device for preparing isobutene by cracking MTBE (such as in the process flow disclosed by USP4,447,668), only by controlling proper ether cracking reaction conditions and selecting proper ether cracking catalysts, proper amounts of dimethyl ether and diisobutylene are contained in ether cracking reaction products,and the production device can produce isobutene and dimethyl ether and diisobutylene products through original separation equipment, so that various useful chemical products can be obtained without increasing equipment investment.
Disclosure of Invention
The invention aims to provide a method for producing isobutene and coproducing dimethyl ether and diisobutylene. The method can be used for producing isobutene, and simultaneously, the content of dimethyl ether and diisobutylene in the obtained product can be adjusted.
In order to achieve the above object, the present invention provides a method for preparing isobutylene and coproducing dimethyl ether and diisobutylene by cracking methyl tert-butyl ether, which comprises the steps of cracking the methyl tert-butyl ether under the action of a solid acid catalyst to obtain isobutylene and methanol, wherein the methanol is further dehydrated and can be converted into dimethyl ether, and the isobutylene is further polymerizedSynthesizing into diisobutylene, separating the cracked product with subsequent equipment to obtain isobutene as main product, dimethyl ether as side product and diisobutylene, and preparing solid acid catalyst with carrier and weak acid inorganic acid salt on the carrier, and the specific surface area of the carrier being at least 25m2A/g, characterized in that the reaction temperature is 230 ℃ and 270 ℃, the conversion of methyl tert-butyl ether is at least 95%, preferably at least 97%, the conversion of methanol is at least 10%, and the conversion of isobutene to diisobutylene is at least 5%.
The pressure and space velocity of the cracking reaction of the methyl tert-butyl ether can be changed in a wide range, and the preferable reaction pressure is 0.2-0.8MPa, and the space velocity is 0.8-2h-1。
When tert-alkyl ether is cracked to prepare isobutene, partial methanol obtained by cracking can be further reacted to generate dimethyl ether by controlling the conversion rate and reaction conditions of MTBE (methyl tert-butyl ether), isobutene is further polymerized to generate diisobutylene, the conversion rate of methanol is controlled to be at least 10%, and the conversion rate of isobutene to generate diisobutylene is controlled to be at least 5%, so that the generation amounts of dimethyl ether and diisobutylene are adjusted to meet the demand of the market for dimethyl ether.
Any solid acid ether cleavage catalyst disclosed in the prior art may be used in the present invention, such as the supported inorganic acid salt catalyst disclosed in GB 1173128.
The catalyst of the present invention may be prepared by any suitable method known in the art, for example, by impregnating the support with a solution of an inorganic acid or a weakly acidic salt of an inorganic acid, followed by drying and calcining. The inorganic acid is preferably sulfuric acid; the weakly acidic inorganic acid salt is preferably a sulfate salt, most preferably ammonium sulfate, ferrous sulfate or ferric sulfate.
The acid radical content of the solid acid catalysts according to the invention can vary within wide limits, for example at least 10 wt.%, preferably from 18 to 32 wt.%, calculated on the support. Most preferably 22 wt.%.
The specific surface area of the carrier is at least 25m2The preferred value of/g is 100-400m2(ii)/g, most preferably 200-2/g。
The carrier may be silica or alumina, such as β -alumina or gamma-alumina, preferably gamma-alumina.
The methyl tert-butyl ether cracking reaction of the invention can be carried out in any ether cracking reactor disclosed in the prior art, and preferably in a tubular fixed bed reactor.
After the ether cracking reaction product is separated by subsequent separation equipment, such as water washing and rectification (lightness and weight removal), an isobutene product, a dimethyl ether product and a diisobutylene product can be obtained.
The present invention is described in detail below:
the MTBE raw material and a heat carrier are subjected to heat exchange and then vaporized and enter a tubular fixed bed reactor, a solid acid catalyst (such as a sulfur acid-containing solid acid catalyst) is filled in the reactor, and the reaction temperature is controlled between 230 ℃ and 270 ℃;the reaction pressure is between 0.2 and 0.8 MPa; the space velocity is 0.8-2h-1(ii) a The conversion of methyl tert-butyl ether is at least 95%,the reacted ether cleavage product mainly contains Isobutene (IB), methanol (MeOH), dimethyl ether (DME), methyl tert-butyl ether (MTBE), Diisobutylene (DIB), water and the like, and the composition of the product is as follows: olefin having 4 carbon atoms (excluding isobutylene) in an amount of about 0.0095%, butane (C4 ℃) in an amount of about 0.0050%, Isobutylene (IB) in an amount of about 54 to 60 wt%, MeOH in an amount of about 15 to 35 wt%, dimethyl ether (DME) in an amount of about 3 to 15 wt%, MTBE in an amount of about 0.5 to 3 wt%, methyl sec-butyl ether (MSBE) in an amount of about 0.1353 wt%, tert-butyl alcohol (TBA) in an amount of about 0.0601 wt%, Diisobutylene (DIB) in an amount of about 3 to 9.2 wt%, triisobutylene (also called triisobutene, abbreviated as TIB) in an amount of about 0.1 to 0.3 wt%, and H2The O content is 1 to 6 (wt%). Separating, washing and rectifying (lightness and weight removal) the ether cracking reaction product by subsequent separation equipment to obtain an isobutene product, a dimethyl ether product and a diisobutylene product.
The invention improves the production process of preparing isobutene by cracking MTBE, so that the qualified isobutene main product can be produced, dimethyl ether and diisobutylene products can be co-produced, and the generation amount of dimethyl ether and diisobutylene can be controlled according to the requirement. The method for producing dimethyl ether can save the equipment investment required by the traditional method for producing dimethyl ether by using methanol as a raw material, and can also improve the conversion rate of methyl tert-butyl ether, thereby improving the utilization rate of equipment; the method can save a diisobutylene reactor and further save equipment investment when simultaneously producing the diisobutylene.
Detailed Description
The present invention is further illustrated by the following examples, without limiting its scope.
The MTBE feedstock used in the following examples had the following composition:
component (wt%)
C4＝0.005
C4° 0.005
IB 0.000
MeOH 0.100
DME 0.000
MTBE 99.348
MSBE 0.142
TBA 0.300
DIB 0.100
TIB 0.000
H2O 0.000
In the following examples the ether cleavage reactor was packed with a solid sulfate-containing acid catalyst having a sulfate content of about 22% by weight. The preparation method comprises the following steps:
examples 1 to 6 the catalysts used were prepared as follows:
dissolving 47 g of analytically pure concentrated sulfuric acid (with the concentration of 98%) in distilled water to prepare 200ml of sulfuric acid aqueous solution, and dissolving 150ml of gamma-Al2O3The carrier was immersed in the above solution for 2 hours, the residual liquid was filtered off, the impregnated carrier was dried at 120 ℃ for 4 hours and then calcined at 550 ℃ for 4 hours, and then the catalyst was further immersed in the above aqueous sulfuric acid solution for 2 hours, and after drying at 120 ℃ for 4 hours and then calcined at 550 ℃ for 4 hours, the sulfate group content in the prepared catalyst was 22.12 wt.%.
The catalyst used in example 7 was prepared as follows:
dissolving 88 g of analytically pure ammonium sulfate in distilled water to prepare 200ml of ammonium sulfate aqueous solution, and dissolving 150ml of gamma-Al2O3The carrier was immersed in the above solution for 2 hours, the residual liquid was filtered off, the impregnated carrier was dried at 120 ℃ for 4 hours and then calcined at 550 ℃ for 4 hours, and the sulfate group content in the prepared catalyst was 22.08 wt.%.
The catalyst used in example 8 was prepared as follows:
83 g of analytically pure ferrous sulfate (FeSO)47H2O) in distilled water to prepare 200ml of ferrous sulfate aqueous solution, and mixing 150ml of gamma-Al2O3The carrier was immersed in the above solution for 2 hours, the residual liquid was filtered off, the impregnated carrier was dried at 120 ℃ for 4 hours, and then calcined at 250 ℃ for 4 hours, and then the catalyst was further immersed in the above ferrous sulfate aqueous solution for 2 hours, and after dried at 120 ℃ for 4 hours, and then calcined at 250 ℃ for 4 hours, and the sulfate group content in the prepared catalyst was 21.97 wt.%.
Example 1
Carrying out ether cracking reaction on MTBE raw material in a tubular reactor filled with a solid acid catalyst containing sulfuric acid, wherein the sulfate content of the used catalyst is 22.12 wt.%, and the reaction temperature is 230 ℃; the reaction pressure is 0.8 MPa; space velocity of 1.2h-1The conversion of MTBE was 98.47%, the conversion of methanol was 12.78%, and the conversion of isobutylene to diisobutylene was 5.09%. Analysis of C4 in the product of the ethereal cleavage reaction by gas chromatography＝0.0095%, C4 ℃ 0.0050%, IB 59.3670 (wt%), MeOH 31.0281 (wt%), DME 3.2685 (wt%), MTBE 1.5230 (wt%), MSBE 0.1353 (wt%), TBA0.0601 (wt%), DIB 3.1670 (wt%) and H2The O content is 1.4365 wt%, and the reaction product is washed with water and rectified to obtain iso-productThe butene had a product purity of 99.720 wt% and contained 5ppm of MTBE, 5ppm of MeOH, 5ppm of DME, 0.276 wt% of C4 (a fraction having 4 carbon atoms except isobutylene, the same applies hereinafter), 5ppm of DIB, and 20ppm of water. And simultaneously obtaining a dimethyl ether product, wherein the dimethyl ether content is 95.20 percent (wt%), the balance is isobutene, and the purity of the obtained diisobutylene product is 97.53 percent, and the balance is MTBE.
Example 2
The MTBE raw material is subjected to ether cracking reaction in a tubular reactor filled with a solid acid catalyst containing sulfuric acid, the catalyst is the same as that in example 1, and the reaction temperature is 240 ℃; the reaction pressure is 0.6 MPa; space velocity of 0.8h-1The conversion of MTBE was 98.63%, the conversion of methanol was 30.59%,the conversion of isobutene to diisobutylene was 9.20%. Analysis of C4 in the product of the ethereal cleavage reaction by gas chromatography＝0.0095%, C4 ℃ 0.0050%, IB 56.7932 (wt%), MeOH 24.7331 (wt%), DME 7.8340 (wt%), MTBE 1.3650 (wt%), MSBE 0.1353 (wt%), TBA0.0601 (wt%), DIB 5.8416 (wt%) and H2The O content was 3.2232 wt%, and the isobutylene product obtained by washing and rectifying the reaction product had a product purity of 99.780 wt%, and contained 5ppm of MTBE, 4ppm of MeOH, 4ppm of DME, the remaining C40.2166 wt%, 3ppm of DIB and 18ppm of water. And meanwhile, a dimethyl ether product is obtained, the dimethyl ether content of the dimethyl ether product is 95.350 wt%, the balance is isobutene, the purity of the obtained diisobutylene product is 97.14%, and the balance is MTBE.
Example 3
The MTBE raw material is subjected to ether cracking reaction in a tubular reactor filled with a solid acid catalyst containing sulfuric acid, the catalyst is the same as that in example 1, and the reaction temperature is 260 ℃; the reaction pressure is 0.4 MPa; space velocity of 1.5h-1The conversion of MTBE was 99.37%, the conversion of methanol was 51.22%, and the conversion of isobutylene to diisobutylene was 11.18%. Analysis of C4 in the product of the ethereal cleavage reaction by gas chromatography＝0.0095%, 0.0050% C4 °, 55.7650 (wt%) IB, 17.5146 (wt%) MeOH, 13.2160 (wt%) DME, 0.6239 (wt%) MTBE, 0.1353 (wt%) MSBE, 0.0601 (wt%) TBA, 7.1250 (wt%) DIB, 0.2160 (wt%) TIB and H2The O content was 5.3296 wt%, and the isobutylene product obtained by washing and rectifying the reaction product had a product purity of 99.750 wt%, and contained 2ppm of MTBE, 5ppm of MeOH, 5ppm of DME, the remaining 40.2464 wt%, 5ppm of DIB and 19ppm of water. And simultaneously obtaininga dimethyl ether product, wherein the dimethyl ether content is 95.430 wt%, the balance is isobutene, the purity of the obtained diisobutylene product is 97.52%, and the balance is MTBE and trimeric isobutene.
Example 4
MTBE raw material in tubular reactor filled with solid acid catalyst containing sulfuric acidThe ether cracking reaction is carried out, the catalyst is the same as that in the example 1, and the reaction temperature is 270 ℃; the reaction pressure is 0.3 MPa; space velocity of 2h-1The conversion of MTBE was 99.52%, the conversion of methanol was 56.22%, and the conversion of isobutylene to diisobutylene was 14.21%. Analysis of C4 in the product of the ethereal cleavage reaction by gas chromatography＝0.0095%, 0.0050% C4 °, 53.8789 (wt%) IB, 15.7435 (wt%) MeOH, 14.5276 (wt%) DME, 0.4762 (wt%) MTBE, 0.1353 (wt%) MSBE, 0.0601 (wt%) TBA, 9.0381 (wt%) DIB, 0.2834 (wt%) TIB and H2The O content is 5.8424 wt%, and the isobutene obtained by washing and rectifying the reaction product has the product purity of 99.710 wt% and contains 4ppm of MTBE, 3ppm of MeOH, 5ppm of DME, the rest of C40.2863 wt%, 5ppm of DIB and 20ppm of water. And simultaneously obtaining a dimethyl ether product, wherein the dimethyl ether content is 95.180 wt%, the balance is isobutene, the purity of the obtained diisobutylene product is 97.38%, and the balance is MTBE and trimeric isobutene.
Example 5
The MTBE raw material is subjected to ether cracking reaction in a tubular reactor filled with a solid acid catalyst containing sulfuric acid, the catalyst is the same as that in example 1, and the reaction temperature is 260 ℃; the reaction pressure is 0.4 MPa; space velocity of 1.2h-1The conversion of MTBE was 99.37%, the conversion of methanol was 51.22%, and the conversion of isobutylene to diisobutylene was 11.18%.Analysis of C4 in the product of the ethereal cleavage reaction by gas chromatography＝0.0095%, 0.0050% C4 °, 55.7649 (wt%) IB, 17.5143 (wt%) MeOH, 13.2163 (wt%) DME, 0.6241 (wt%) MTBE, 0.1353 (wt%) MSBE, 0.0601 (wt%) TBA, 7.1252 (wt%) DIB, 0.2162 (wt%) TIB and H2The O content was 5.3291 wt%, and the isobutylene product obtained by washing and rectifying the reaction product had a product purity of 99.750 wt%, and contained 2ppm of MTBE, 5ppm of MeOH, 5ppm of DME, the remaining 40.2464 wt%, 5ppm of DIB and 19ppm of water. Simultaneously obtaining a dimethyl ether product, wherein the dimethyl ether content is 95.430 wt percent, the balance is isobutene, and the purity of the obtained diisobutylene product is97.72%, the balance being MTBE and trimerized isobutene.
Example 6
The MTBE raw material is subjected to ether cracking reaction in a tubular reactor filled with a solid acid catalyst containing sulfuric acid, the catalyst is the same as that in example 1, and the reaction temperature is 260 ℃; the reaction pressure is 0.6 MPa; space velocity of 1.5h-1，The conversion of MTBE was 99.37%, the conversion of methanol was 51.22%, and the conversion of isobutylene to diisobutylene was 11.18%. Analysis of C4 in the product of the ethereal cleavage reaction by gas chromatography＝0.0095%, 0.0050% C4 °, 55.7664 (wt%) IB, 17.5150 (wt%) MeOH, 13.2158 (wt%) DME, 0.6236 (wt%) MTBE, 0.1353 (wt%) MSBE, 0.0601 (wt%) TBA, 7.1247 (wt%) DIB, 0.2154 (wt%) TIB and H2The O content was 5.3292 wt%, and the isobutylene product obtained by washing and rectifying the reaction product had a product purity of 99.750 wt%, and contained 2ppm of MTBE, 5ppm of MeOH, 5ppm of DME, the remaining 40.2464 wt%, 5ppm of DIB and 19ppm of water. And simultaneously obtaining a dimethyl ether product, wherein the dimethyl ether content is 95.430 wt%, the balance is isobutene, the purity of the obtaineddiisobutylene product is 97.19%, and the balance is MTBE and trimeric isobutene.
Example 7
The MTBE raw material is subjected to ether cracking reaction in a tubular reactor filled with a solid acid catalyst containing sulfate, and the sulfate content of the used catalyst is 22.08%. The reaction temperature is 260 ℃; the reaction pressure is 0.4 MPa; space velocity of 2h-1The conversion of MTBE was 97.83%, the conversion of methanol was 51.89%, and the conversion of isobutylene to diisobutylene was 11.32%. Analysis of C4 in the product of the ethereal cleavage reaction by gas chromatography＝0.0095%, 0.0050% C4 °, 54.8125 (wt%) IB, 17.0047 (wt%) MeOH, 13.1826 (wt%) DME, 2.1539 (wt%) MTBE, 0.1353 (wt%) MSBE, 0.0601 (wt%) TBA, 7.0987 (wt%) DIB, 0.2216 (wt%) TIB and H2The O content is 5.3161 (wt%), the isobutene obtained by washing and rectifying the reaction product has the product purity of 99.750(wt)% of these contains 2ppm of MTBE, 5ppm of MeOH, 5ppm of DME, the remainder of C40.2464 (wt%), 5ppm of DIB and 19ppm of water. And simultaneously obtaining a dimethyl ether product, wherein the dimethyl ether content is 95.350 wt%, the balance is isobutene, the purity of the obtained diisobutylene product is 97.27%, and the balance is MTBE and trimeric isobutene.
Example 8
The above MTBE feedstock was subjected to ether cleavage in a tubular reactor containing a solid acid sulfate-containing catalyst having a sulfate content of 21.97%. The preparation method is described in detail above, and the reaction temperature is 260 ℃; the reaction pressure is 0.3 MPa; space velocity of 1.5h-1The conversion of MTBE was 97.22%, the conversion of methanol was 52.11%, and the conversion of isobutylene to diisobutylene was 11.35%. Analysis of C4 in the product of the ethereal cleavage reaction by gas chromatography＝0.0095% C4 ℃ 0.0050%, IB 54.4355 (wt%), MeOH 16.8226 (wt%), DME 13.1538 (wt%),2.7649 (wt%) MTBE content, 0.1353 (wt%) MSBE content, TBA0.0601 (wt%), DIB content 7.0756 (wt%), TIB content 0.2329 (wt%) and H2The O content was 5.3048 wt%, and the isobutylene product obtained by washing and rectifying the reaction product had a product purity of 99.710 wt%, and contained 4ppm of MTBE, 3ppm of MeOH, 5ppm of DME, the remaining C40.2863 wt%, 5ppm of DIB and 20ppm of water. And simultaneously obtaining a dimethyl ether product, wherein the dimethyl ether content is 95.350 wt%, the balance is isobutene, the purity of the obtained diisobutylene product is 97.61%, and the balance is MTBE and trimeric isobutene.
Claims (10)
1. A process for preparing isobutylene and dimethyl ether and diisobutylene by cracking methyl tert-butyl ether includes such steps as cracking methyl tert-butyl ether in the presence of solid acidic catalyst to obtain isobutylene and methanol, dewatering methanol to convert it to dimethyl ether, polymerizing isobutylene to obtain diisobutylene, separating the cracked product by subsequent equipment to obtain isobutylene as main product, dimethyl ether as by-product and diisobutylene as by-product, and catalytic reaction of solid acidThe agent comprises a carrier having a specific surface of at least 25m and a weakly acidic metal-containing component supported thereon2A/g, characterized in that the reaction temperature is 230-270 ℃, the conversion of methyl tert-butyl ether is at least 95%, the conversion of methanol is at least 10%, and the conversion of isobutene to diisobutylene is at least 5%.
2. The method according to claim 1, wherein the cracking reaction pressure of the methyl tert-butyl ether is 0.2-0.8MPa, and the space velocity is 0.8-2h-1。
3. A process according to claim 1 or 2 characterised in that the weakly acidic metal-containing component is formed by impregnating the support with a salt of an inorganic acid or a weakly acidic inorganic acid.
4. The method of claim 3, wherein the mineral acid is sulfuric acid.
5. A process according to claim 3, characterised in that the weakly acidic inorganic acid salt is a sulphate salt, preferably ammonium sulphate, ferrous sulphate or ferric sulphate.
6. A method according to any of claims 1-5, characterized in that the acid content of the solid acid catalyst is 18-32 wt.%, preferably 22 wt.%, calculated on the support.
7. The method according to any one of claims 1 to 6, wherein the specific surface area of the carrier is 100-400m2G, preferably 200-300m2/g。
8. A process according to any one of claims 1 to 7, characterised in that the support is gamma-alumina.
9. The process according to any one of claims 1 to 8, characterized in that the conversion of methyl tert-butyl ether is at least 97%.
10. The process according to any one of claims 1 to 9, characterized in that the reaction is carried out in a tubular fixed bed reactor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381273B (en) * | 2007-09-06 | 2012-08-22 | 四川古杉油脂化学有限公司 | Method for preparing isobutene by tert-butanol and apparatus |
| CN104447165A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Method for producing isobutene and dipolyisobutylene through cracking of methyl tert-butyl ether |
| CN105478164A (en) * | 2015-11-26 | 2016-04-13 | 王金明 | Preparation method of catalyst for production of isobutene |
-
2002
- 2002-11-01 CN CN 02146148 patent/CN1202051C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381273B (en) * | 2007-09-06 | 2012-08-22 | 四川古杉油脂化学有限公司 | Method for preparing isobutene by tert-butanol and apparatus |
| CN104447165A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Method for producing isobutene and dipolyisobutylene through cracking of methyl tert-butyl ether |
| CN104447165B (en) * | 2013-09-16 | 2016-04-27 | 中国石油化工股份有限公司 | The method of iso-butylene and Diisobutylene is produced in a kind of methyl tertiary butyl ether cracking |
| CN105478164A (en) * | 2015-11-26 | 2016-04-13 | 王金明 | Preparation method of catalyst for production of isobutene |
| CN105478164B (en) * | 2015-11-26 | 2018-03-02 | 王金明 | A kind of preparation method for producing isobutene catalyst |
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| CN1202051C (en) | 2005-05-18 |
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