CN100467124C - Catalyst for producing isobutene by cracking methyl tert-butyl ether - Google Patents
Catalyst for producing isobutene by cracking methyl tert-butyl ether Download PDFInfo
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- CN100467124C CN100467124C CNB021511489A CN02151148A CN100467124C CN 100467124 C CN100467124 C CN 100467124C CN B021511489 A CNB021511489 A CN B021511489A CN 02151148 A CN02151148 A CN 02151148A CN 100467124 C CN100467124 C CN 100467124C
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- catalyst
- butyl ether
- isobutene
- methyl
- cracking
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Abstract
The composition of solid acid catalyst for preparing isobutylene by cracking reaction of methyl tert-butyl ether contains (wt%) 20-95% of aluminium oxide, 0.1-20% of titanium dioxide, 0-5% of other oxide and 0.5-50% of loaded SO4, and its preparation method includes the following steps: adding aluminium oxide into the aqueous solution containing Ti(SO4)2 and other soluble metal salt, filtering, soaking filter cake in ammonia water, filtering, washing, drying, soaking in sulfuric acid solution, filtering, drying and baking so as to obtain the invented SO4/M-TiO2/Al2O3 type low-temp. catalyst.
Description
Technical field
The present invention relates to a kind ofly be used for methyl tertiary butyl ether(MTBE) cracking reaction preparing isobutene catalyst, and preparation method and application, the particularly solid acid catalyst that be used for methyl tertiary butyl ether(MTBE) cracking reaction preparing isobutene of active constituent loading on alumina support.
Background technology
Isobutene is a kind of important Organic Chemicals.For decades recently, its social demand amount is all the time at rapid growth.It not only can be used for the manufacturing of gasoline and lube oil additive, but also can be used as the important auxiliary agent and the raw material of other chemical products, is used for preparing the number of chemical product, also is synthetic primary raw material such as agricultural chemicals, coating, antioxidant, water stabilizing agent.Therefore, very active to the research of the industrialized preparing process of isobutene in recent decades.The preparation method of isobutene is a lot, mainly contains several different methods such as sulfuric acid extraction, direct hydration method, catalytic cracking method, butane isomery dehydriding, n-butene skeletal isomerization method, tert-butyl alcohol evaporation and etherification method.Etherification method is that the isobutene highly selective reaction in methyl alcohol (or other primary alconol) and the hybrid C 4 cut generates after the methyl tertiary butyl ether(MTBE), carries out cracking again.Because methyl tertiary butyl ether(MTBE) cracking reaction conversion ratio and selectivity are all very high, reactant promptly can obtain highly purified isobutene through distillation and washing.The methyl tertiary butyl ether(MTBE) synthesis technique matches with cracking technology, formed the process route that advanced carbon four separates and prepare high-purity isobutylene, making etherification method prepare isobutene has become maximum, most widely used, the most attractive a kind of methods of research in the present preparation isobutene method.
Catalyst is the key that etherification method prepares isobutene, and the quality of catalyst directly has influence on important indicators such as the conversion ratio, selectivity of reaction.The catalyst of this method has: alumina system (USP 3170000), silica system (CN1056299), ion exchange resin system (USP 4447668), sulfate system (BP P 1482883), molecular sieve system (USP4566016), heteropolyacid system (CN1185992) and other some catalyst based on solid acid catalyst at present.But they all more or less have a following variety of issue:
The better heat stability of methyl tertiary butyl ether(MTBE), cracking need be carried out under higher temperature, though but improve the raising that reaction temperature helps methyl tertiary butyl ether(MTBE) cracking conversion ratio, and also help the generation of side reaction simultaneously, cause the loss of product isobutene as the isobutene dimerization; The generation of dimethyl ether can reduce the rate of recovery of methyl alcohol, causes adding a large amount of methyl alcohol in initial etherification reaction system again; The water and the isobutene hydration that produce when dimethyl ether generates also make product suffer a loss, and the generation of the accessory substance tert-butyl alcohol has simultaneously increased cost for the separation and purification of product, or the like.Higher reaction temperature has also been brought difficulty to operation, has increased energy consumption.Above-mentioned catalyst is high to methyl tertiary butyl ether(MTBE) cracking conversion ratio, but need add a large amount of inert substances such as water vapour during reaction, the rate of recovery and the utilization rate of equipment and installations of methyl alcohol and isobutene have reduced widely, make that its process is complicated, and cause expensive surcharge.The shortcoming of ion-exchange resin catalyst is that resistance to elevated temperatures is relatively poor, and when the temperature of reaction was too high, sulfonic acid group wherein came off easily, owing to be subjected to the restriction of reaction temperature, the conversion ratio of reaction is all lower.The deadly defect of sulfate system catalyst is under reaction condition, and sulfate will decompose gradually, thereby causes the corrosion of equipment and the decline of catalyst activity.
Therefore, provide a kind of under lower reaction temperature, have high conversion ratio, high isobutene and methyl alcohol optionally the methyl tertiary butyl ether(MTBE) catalyst for cracking be related industry department very expectation.
Summary of the invention
One of technical issues that need to address of the present invention are to disclose a kind of cracking isobutene by methyl-tert-butyl ether catalyst, to overcome the above-mentioned defective that prior art exists, satisfy the demand of related industry department;
Two of the technical issues that need to address of the present invention are to disclose described Preparation of catalysts method;
Another technical issues that need to address of the present invention are to disclose above-mentioned Application of Catalyst method.
Technical conceive of the present invention is:
The methyl tertiary butyl ether(MTBE) cracking is the back reaction of methyl tertiary butyl ether(MTBE) synthetic reaction, under the acidic catalyst effect, is cracked into isobutene and methyl alcohol.
Following main side reaction also may take place during the methyl tertiary butyl ether(MTBE) cracking:
A. the isobutene dimerization generates Diisobutylene
B. the isobutene hydration generates the tert-butyl alcohol
C. methanol dehydration generates dimethyl ether
Above-mentioned reaction all is reversible reaction, the growing amount and the reaction temperature of methyl tertiary butyl ether(MTBE) cracking conversion ratio and accessory substance have confidential relation, improving reaction temperature can increase the equilibrium constant of main reaction, improve the conversion ratio of methyl tertiary butyl ether(MTBE), but also quickened the generation of side reaction, in order to improve the selectivity of main reaction product (isobutene and methyl alcohol), suppress the generation of side reaction, the inventor thinks, if can under lower reaction temperature, prepare isobutene by decomposition of methyl tertiary-butyl ether, above-mentioned side reaction just can be suppressed effectively, some reaction even no longer generation are to guarantee that high isobutene and methyl alcohol selectivity are arranged, simultaneously, by improving activity of such catalysts, to guarantee to have high methyl tertiary butyl ether(MTBE) cracking conversion ratio, under the condition that guarantees the first two purpose of realization, do not need in methyl tertiary butyl ether(MTBE) cracking reaction system, to add the inert substance of entry and so on, to cut down the consumption of energy, improve utilization rate of equipment and installations.For this reason, the inventor studies the needed catalyst of course of reaction, has proposed a kind of multicomponent SO that is carried on the alumina support
4/ M-TiO
2/ Al
2O
3Type solid acid catalyst (wherein M is Zr, Sn, Zn, one or both among Si or the Ca) is used for the low temperature pyrolyzer course of reaction of methyl tertiary butyl ether(MTBE).
Technical scheme of the present invention:
Catalyst of the present invention is a kind of composition, and its component and weight percent content comprise:
Alundum (Al 20～95%
Titanium dioxide 0.1～20%
Other oxides 0～5%
The SO of load
4 =0.5～50%
Said alundum (Al comprises hydrated alumina, γ-Al
2O
3, η-Al
2O
3Or θ-Al
2O
3Deng in a kind of, preferred γ-Al
2O
3Other oxides can be zirconias, tin oxide, zinc oxide, one or both in silica or the barium monoxide.
Above-mentioned Preparation of catalysts comprises the steps:
Alundum (Al joined contain Ti (SO
4)
2With the soluble-salt of M (wherein M is Zr,, Sn, Zn, one or both among Si or the Ca) in the aqueous solution, filter, filter cake is dipped in ammoniacal liquor, filters, wash to pH be 7.5～11, dry, impregnated in sulfuric acid solution then, filter drying, in 200～800 ℃ of following roastings 3～8 hours, promptly obtain SO of the present invention
4/ M-TiO
2/ Al
2O
3The type low temperature catalyst.
According to the present invention, Ti (SO
4)
2The weight concentration of the aqueous solution is 0.5～50%, and optimum scope is 2～30%.The weight concentration of other oxide water solutions is 0～5%, and optimum scope is 0.1～3%.
Sulfuric acid concentration is 0.05～15N, and optimum scope is 0.1～5N.
Use catalyst of the present invention to carry out the cracking isobutene by methyl-tert-butyl ether reaction, desired reaction temperature is generally 100～280 ℃, optimal reaction temperature is 120～200 ℃, reaction pressure is 0～2MPa, from economic angle and the simple and easy consideration of operation, the general saturated vapor of isobutene when condensation temperature that all equal at least depressed and operated, so optimum response pressure is 0.2～1.0Mpa.The flow velocity of methyl tertiary butyl ether(MTBE) with the per hour liquid feed volume of per volume of catalyst (liquid air speed) expression, is generally 0.1～10h
-1, the optimal liquid air speed is 0.5～6h
-1
Prepare isobutene and methyl alcohol as stated above, the rate of recovery of isobutene and methyl alcohol can be near 100%.
By above-mentioned disclosed technical scheme as seen, catalyst of the present invention can carry out the methyl tertiary butyl ether(MTBE) cracking reaction at low temperatures, has high isobutene and methyl alcohol optionally simultaneously, high methyl tertiary butyl ether(MTBE) cracking conversion ratio is also arranged, do not need simultaneously in methyl tertiary butyl ether(MTBE) cracking reaction system, to add the inert substance of entry etc., energy consumption is low, the utilization rate of equipment and installations height.
The specific embodiment
The following examples will further be illustrated the present invention, but be limited the scope of the invention anything but.
Embodiment 1
Gama-alumina joined 10% Ti (SO
4)
2In 1% the zirconyl nitrate aqueous solution, standing over night.After the filtration, be immersed in the ammoniacal liquor, elimination ammoniacal liquor, put into deionized water wash to pH be 8.5, filter cake in 130 ℃ of baking ovens dry 5 hours.At room temperature leave standstill dipping with excessive 2N sulfuric acid solution, put into 110-150 ℃ baking oven inner drying 3 hours behind the suction filtration again, after 800 ℃ of roastings, obtain catalyst.
20 gram catalyst are packed in the micro fixed-bed reactor of Φ 20 mm dias, methyl tertiary butyl ether(MTBE) micro pump charging, controlling the liquid air speed is 2h
-1, 130 ℃ of reaction temperatures, methyl tertiary butyl ether(MTBE) conversion ratio 98%, selective isobutene 99%, methyl alcohol selectivity 99%.
Embodiment 2
Gama-alumina joined 5% Ti (SO
4)
2In the aqueous solution, standing over night.After the filtration, be immersed in the ammoniacal liquor, elimination ammoniacal liquor, put into deionized water wash to pH be 8, filter cake in 150 ℃ of baking ovens dry 5 hours.At room temperature leave standstill dipping with excessive 1N sulfuric acid solution, put into 110 ℃ baking oven inner drying 3 hours behind the suction filtration again, after 800 ℃ of roastings, obtain catalyst.
20 gram catalyst are packed in the micro fixed-bed reactor of Φ 20 mm dias, methyl tertiary butyl ether(MTBE) micro pump charging, controlling the liquid air speed is 2h
-1, 150 ℃ of reaction temperatures, methyl tertiary butyl ether(MTBE) conversion ratio 96%, different ` butylene selectivity 99%, methyl alcohol selectivity 99%.
Claims (8)
1. the cracking isobutene by methyl-tert-butyl ether catalyst is characterized in that, percentage by weight consists of:
Alundum (Al 20～95%
Titanium dioxide 0.1～20%
Other oxide 0～5%
The SO of load
4 =0.5～50%
The percentage by weight sum of forming is 100%;
Other oxides are zirconias, tin oxide, zinc oxide, one or both in silica or the barium monoxide.
2. catalyst according to claim 1 is characterized in that alundum (Al is hydrated alumina, γ-Al
2O
3, η-Al
2O
3Or θ-Al
2O
3In a kind of.
3. catalyst according to claim 2 is characterized in that alundum (Al is γ-Al
2O
3
4. according to claim 1,2 or 3 described Preparation of catalysts methods, it is characterized in that comprising the steps:
Alundum (Al is added Ti (SO
4)
2In the aqueous solution of the soluble-salt of M, filter, filter cake is dipped in ammoniacal liquor, filters, wash to pH be 7.5～11, drying impregnated in sulfuric acid solution then, filters, drying in 200～800 ℃ of following roastings, promptly obtains the cracking isobutene by methyl-tert-butyl ether catalyst;
M is Zr, Sn, Zn, one or both among Si or the Ba.
5. preparation method according to claim 4 is characterized in that sulfuric acid concentration is 0.05～15N.
6. preparation method according to claim 5 is characterized in that sulfuric acid concentration is 0.1～5N.
7. according to claim 1,2 or 3 described Application of Catalyst, it is characterized in that being used for cracking isobutene by methyl-tert-butyl ether.
8. application according to claim 7 is characterized in that reaction temperature is 100～280 ℃, and reaction pressure is 0～2MPa, and the flow velocity of methyl tertiary butyl ether(MTBE) is expressed as 0.1～10h with the liquid feed volume of per volume of catalyst per hour
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021511489A CN100467124C (en) | 2002-12-06 | 2002-12-06 | Catalyst for producing isobutene by cracking methyl tert-butyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021511489A CN100467124C (en) | 2002-12-06 | 2002-12-06 | Catalyst for producing isobutene by cracking methyl tert-butyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1418729A CN1418729A (en) | 2003-05-21 |
| CN100467124C true CN100467124C (en) | 2009-03-11 |
Family
ID=4751934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021511489A Expired - Fee Related CN100467124C (en) | 2002-12-06 | 2002-12-06 | Catalyst for producing isobutene by cracking methyl tert-butyl ether |
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|---|---|
| CN (1) | CN100467124C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441287C (en) * | 2002-04-18 | 2008-12-10 | 触媒化成工业株式会社 | Titania powder for honeycomb waste gas treating catalyst, and waste gas treating catalyst |
| CN100420518C (en) * | 2006-09-08 | 2008-09-24 | 华东理工大学 | Catalyst of solid acid in use for preparing isobutene, and preparation method |
| CN106031876B (en) * | 2015-03-19 | 2019-05-10 | 华东理工大学 | The catalyst and preparation method thereof of isobutene is prepared for ether-splitting solution |
| CN106622302A (en) * | 2016-11-29 | 2017-05-10 | 华东理工大学 | Preparation method of catalyst for preparation of high-purity olefin |
| CN106955687B (en) * | 2017-03-18 | 2019-11-01 | 华东理工大学 | A kind of preparation method and application of the catalyst being used to prepare alkene |
| CN109928859B (en) * | 2017-12-15 | 2021-07-23 | 万华化学集团股份有限公司 | Treatment method of isobutene refining kettle residues |
| CN108409517B (en) * | 2018-02-24 | 2020-10-20 | 安徽海德化工科技有限公司 | Method for preparing isobutene by catalytic cracking of methyl tert-butyl ether |
| CN109225349B (en) * | 2018-10-30 | 2021-07-09 | 蚌埠知博自动化技术开发有限公司 | Preparation method of catalyst for preparing isobutene by cracking methyl tert-butyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1165479A (en) * | 1968-07-09 | 1969-10-01 | Shell Int Research | Process for the Preparation of Tertiary Monoolefins |
| GB1173128A (en) * | 1968-09-20 | 1969-12-03 | Shell Int Research | Process for the preparation of Olefins |
-
2002
- 2002-12-06 CN CNB021511489A patent/CN100467124C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1165479A (en) * | 1968-07-09 | 1969-10-01 | Shell Int Research | Process for the Preparation of Tertiary Monoolefins |
| GB1173128A (en) * | 1968-09-20 | 1969-12-03 | Shell Int Research | Process for the preparation of Olefins |
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| Publication number | Publication date |
|---|---|
| CN1418729A (en) | 2003-05-21 |
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Assignee: Shanghai Huayi Acrylic Acid Co., Ltd. Assignor: East China University of Science and Technology Contract record no.: 2011310000255 Denomination of invention: Catalyst for producing isobutene by cracking methyl tert-butyl ether Granted publication date: 20090311 License type: Common License Open date: 20030521 Record date: 20111227 |
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Granted publication date: 20090311 Termination date: 20161206 |