CN103846098B - Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene - Google Patents

Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene Download PDF

Info

Publication number
CN103846098B
CN103846098B CN201410111268.2A CN201410111268A CN103846098B CN 103846098 B CN103846098 B CN 103846098B CN 201410111268 A CN201410111268 A CN 201410111268A CN 103846098 B CN103846098 B CN 103846098B
Authority
CN
China
Prior art keywords
poms
amylene
iso
catalyst
tame
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410111268.2A
Other languages
Chinese (zh)
Other versions
CN103846098A (en
Inventor
王筠松
陆文龙
李运运
欧恒
卢冠忠
郭杨龙
郭耘
王艳芹
詹望成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN201410111268.2A priority Critical patent/CN103846098B/en
Publication of CN103846098A publication Critical patent/CN103846098A/en
Application granted granted Critical
Publication of CN103846098B publication Critical patent/CN103846098B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of multicomponent X/Z for the preparation of high-purity iso-amylene2O3/POMs/Al2O3Type Catalysts and its preparation method. According to the method, the component of catalyst and percentage by weight are: Al2O3？20~95%，Z2O3？0.01~20%,POMs？0.01~50%，X0.01 ~ 25%. Catalyst of the present invention can (140 ~ 160 DEG C) carry out the reaction of tert amyl methyl ether(TAME) cracking for iso-amylene at than the lower temperature of current similar catalyst, ensureing that high iso-amylene and methyl alcohol are optionally simultaneously, tert amyl methyl ether(TAME) cracking approaches completely and transforms, the similar industrial catalyst of liquid-containing air speed ratio of reaction has the raising of 2 ~ 5 times, do not need to the tert amyl methyl ether(TAME) cracking reaction system inert substance such as add water simultaneously, do not changing under the condition of existing consersion unit, can make Energy Intensity Reduction in suitability for industrialized production, utilization rate of equipment and installations significantly improves.

Description

Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene
Technical field
The present invention relates to preparation and the application of a kind of tert amyl methyl ether(TAME) (TAME) cracking for iso-amylene catalyst. MainlyWhat relate to is rare earth oxide, and heteropoly acid and salt thereof and halogen load on the multicomponent X/Z on alundum (Al2O3)2O3/POMs/Al2O3Type catalyst.
Background technology
Iso-amylene is the mixture of 2-methyl-2-butene (2M2B) and 2-methyl-1-butene alkene (2M1B), is important essenceRefinement work intermediate feed, mainly for the production of isoprene, pinacoline (methyl tertbutyl ketone), tert-pentyl alcohol and spices, farmingThe protective agent of thing, also can be used as the intermediate of synthetic rubber, resin and organic synthesis, wherein accounts for for the production of agricultural chemicals and spicesThe overwhelming majority. Because the downstream product of iso-amylene is a lot, iso-amylene is in great demand China, particularly along with domestic phosphorousThe forbidding of agricultural chemicals, iso-amylene is as the base of the non-phosphorous agricultural chemicals such as synthetic triazole bactericidal agent, plant growth regulator and herbicideThis raw material is used widely, and demand increases rapidly.
Iso-amylene is mainly present in the by-product C5 fraction of catalytic cracking (FCC) gasoline and cracking ethylene preparation, industrial lifeThe method of producing iso-amylene mainly contains the techniques such as sulfuric acid extraction, TAME ether solution, isopentane dehydriding, linear alkene isomerate process.Tert amyl methyl ether(TAME) (TAME) cracking is the technique that a kind of advanced technology and economically viable new development are got up for iso-amylene, withTraditional handicraft is compared, and has the features such as pollution-free, corrosion-free, product purity is high, conversion per pass is high, device independence is strong, quiltApplication widely.
Catalyst is the key that ether solution is prepared iso-amylene, and the performance of catalyst directly has influence on the conversion of ether solution reactionThe important indicator such as rate, selectivity of product.
From reacting itself, tert amyl methyl ether(TAME) cracking is the endothermic reaction, improves reaction temperature and is conducive to methyl-tert pentaBase ether-splitting solution generates iso-amylene, and when temperature is higher, TAME approaches completely and transforms, and has avoided the separation recycling of TAME etc.Problem, has reduced energy consumption. But when cracking temperature is high, side reaction increases, as iso-amylene, oligomerisation causes the loss of iso-amylene; Cracking obtainsThe methanol dehydration arriving generates dimethyl ether, and the generation of dimethyl ether can reduce the rate of recovery of methyl alcohol, causes adding a large amount of first againAlcohol is in initial etherification reaction system; The water and the iso-amylene hydration that when dimethyl ether generates, produce also make product lost, withTime accessory substance tert-pentyl alcohol generation increased cost etc. to the separation and purification of product.
Therefore provide a kind of under lower reaction temperature, have high conversion ratio, high air speed, high iso-amylene and methyl alcoholOptionally tert amyl methyl ether(TAME) catalyst for cracking is that related industry department is extremely expected.
Summary of the invention
Tert amyl methyl ether(TAME) cracking is the back reaction of tert amyl methyl ether(TAME) synthetic reaction, under catalyst action, is cracked intoIso-amylene and methyl alcohol.
When tert amyl methyl ether(TAME) cracking, also may there is following main side reaction:
1. the oligomerisation reaction of iso-amylene
2. methanol dehydration generates dimethyl ether
3. tert-pentyl alcohol dehydration
Above-mentioned reaction is all reversible reaction, the growing amount of tert amyl methyl ether(TAME) cracking conversion ratio and accessory substance and reaction temperatureHave close relationship, improving reaction temperature can increase the equilibrium constant of main reaction, improves the conversion ratio of tert amyl methyl ether(TAME), butAlso accelerated the generation of side reaction, in order to improve the selective of main reaction product (iso-amylene and methyl alcohol), suppressed side reaction simultaneouslyGeneration, if decomposition of methyl tert-amyl ether is prepared iso-amylene under lower reaction temperature, above-mentioned side reaction just can be hadThe inhibition of effect, some reaction even no longer occurs, to ensure high iso-amylene and methyl alcohol selective, improves catalyst simultaneouslyActivity, to ensure high TAME cracking conversion ratio and reaction velocity.
Therefore the object of the invention is ensureing high methyl alcohol and iso-amylene selectively and the conversion ratio of tert amyl methyl ether(TAME)Under prerequisite, provide a kind of in the situation that other process conditions are substantially constant, reaction temperature can be reduced, tert amyl methyl ether(TAME)The catalyst that volume space velocity significantly improves.
For this reason, inventor studies the needed catalyst of course of reaction, has proposed a kind of novel load in oxidationThe multicomponent X/Z of alumina supporter2O3/POMs/Al2O3Type catalyst, for the low temperature ether solution course of reaction of tert amyl methyl ether(TAME), splitsSeparate the inert substance that reaction does not need to add water and so in tert amyl methyl ether(TAME) cracking reaction system, can greatly reduce energy consumption,Volume space velocity significantly improves, and has improved utilization rate of equipment and installations.
Multicomponent X/Z2O3/POMs/Al2O3Type solid acid catalyst, its constituent mass degree is:
Al2O320~95%
POMs0.01~50%
Z2O30.01~20%
X0.01~25%
Said Al2O3For alundum (Al2O3), derive from hydrated alumina, γ-Al2O3、η-Al2O3Or θ-Al2O3In oneKind, preferably γ-Al2O3, POMs is heteropoly acid and salt thereof, derives from phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, silicotungstic heteropolyacid, silicon molybdenumOne in heteropoly acid and relevant salt thereof; Z2O3For rare earth or metal oxide, derive from rare earth element ce, La, Sm and Zr etc.One in the aqueous solution salt of metal; X is halogen, derives from ammonium fluoride, sodium fluoride, hydrofluoric acid, ammonium chloride, sodium chloride, halogenationOne in the aqueous solution of thing.
The preparation of above-mentioned catalyst comprises the steps:
By Al2O3Be immersed in configured containing in the aqueous solution of POMs 1 ~ 8 hour, filter, then in 200 ~ 800 DEG CRoasting 2 ~ 8 hours, obtains POMs/Al2O3；
To obtain POMs/Al2O3Join in the rare earths salt having configured and flood 1 ~ 8 hour, filter, in 80 ~180 DEG C dry 2 ~ 10 hours, then 300 ~ 800 DEG C of roastings 2 ~ 10 hours, obtain Z2O3/POMs/Al2O3；
To obtain Z2O3/POMs/Al2O3Join in halide solution and flood 1 ~ 8 hour, filter, in 80 ~ 180 DEG CDry 2 ~ 10 hours, then 200 ~ 800 DEG C of roastings 2 ~ 10 hours, obtained the multicomponent X for the preparation of iso-amylene-/Z2O3/POMs/Al2O3Type catalyst.
According to the present invention, the concentration of the water-soluble salt solution of rare earth and metal oxide is 0.1 ~ 20%, optimum modelEnclose is 0.5 ~ 15%. The concentration of POMs solution is 0.1 ~ 50%, and optimum concentration is 1 ~ 30%. The concentration of halide solution is0.01 ~ 40%, optimum concentration is 0.5 ~ 15%. Al in the POMs aqueous solution2O3Amount be 0.1 ~ 10g/ml; Rare earth salt aqueous solutionMiddle POMs/Al2O3Amount be 0.01 ~ 30g/ml; Z in halide solution2O3/POMs/Al2O3Amount be 0.1 ~ 30g/ml.
Use multicomponent X/Z2O3/POMs/Al2O3When type catalyst decomposition of methyl tert-amyl ether is prepared iso-amylene reaction,Required reaction temperature is generally 100 ~ 400 DEG C, and optimal reaction temperature is 120 ~ 220 DEG C, and reaction pressure is 0.1 ~ 1MPa, from warpJi angle and the simple and easy consideration of operation, generally at least equal the saturated vapor of iso-amylene in the time of condensation temperature and depress and operate, instituteTaking optimum response pressure as 0.1 ~ 1.0MPa. The flow velocity of tert amyl methyl ether(TAME), enters with the liquid of per volume of catalyst per hourMaterial volume (liquid air speed) represents, is generally 0.1 ~ 20h-1, optimal liquid air speed is 0.5 ~ 15h-1。
From above-mentioned disclosed technical scheme, the invention has the advantages that catalyst can be at lower temperature (120 ~220 DEG C) carry out tert amyl methyl ether(TAME) cracking reaction, TAME approaches completely and transforms; Iso-amylene be selectively 100%, the choosing of methyl alcoholSelecting property is more than 99.5%. Use catalyst of the present invention, along with the variation of reaction condition, 2-methyl-1-butene alkene accounts for iso-amyleneThe ratio of (mixture of 2-methyl-2-butene and 2-methyl-1-butene alkene) can be controlled between 20 ~ 50%.
Detailed description of the invention
The following examples will further be described the present invention, but never limit the scope of the invention.
Embodiment 1
By 30 grams of γ-Al2O3Join in 50ml20% Salkowski's solution and under room temperature, leave standstill 4h, then filter, 100 DEG C dryDry 2h, obtains POMs/Al at 300 DEG C of roasting 6h2O3。
Then La (the NO that is 18% by product in 40ml concentration3)3In the aqueous solution, dipping 6h, after filtration, 100 DEG C are dry8h, obtains La at 500 DEG C of roasting 8h2O3/POMs/Al2O3。
Again by La2O3/POMs/Al2O3Join 50ml concentration and be in 20% ammonium fluoride solution, filter, 100 DEG C dry2h, at 500 DEG C of roasting 5h, obtains F/La of the present invention2O3/POMs/Al2O3。
14g catalyst is packed in the micro fixed-bed reactor of Φ 20mm diameter into tert amyl methyl ether(TAME) micro-amounts of liquidsSampling pump charging, controlling liquid air speed is 2.5h-1, reaction temperature is 155 DEG C, TAME conversion ratio 99.2%, and iso-amylene is selective99.8%, methyl alcohol selective 99.8%. 2-methyl-1-butene alkene accounts for iso-amylene (mixing of 2-methyl-2-butene and 2-methyl-1-butene alkeneCompound) ratio 21%.
Embodiment 2
By 30 grams of γ-Al2O3Join in 50ml15% Salkowski's solution and under room temperature, leave standstill 4h, then filter, 100 DEG C dryDry 2h, obtains POMs/Al at 300 DEG C of roasting 6h2O3。
Then Ce (the NO that is 1% by product in 40ml concentration3)3In the aqueous solution, dipping 2h, after filtration, 150 DEG C of dry 1h,Obtain Ce at 500 DEG C of roasting 4h2O3/POMs/Al2O3。
Again by Ce2O3/POMs/Al2O3Join 25ml concentration and be in 10% Fluorinse, filter, 120 DEG C dry5h, at 500 DEG C of roasting 5h, obtains F/Ce of the present invention2O3/POMs/Al2O3。
14g catalyst is packed in the micro fixed-bed reactor of Φ 20mm diameter into tert amyl methyl ether(TAME) micro-amounts of liquidsSampling pump charging, controlling liquid air speed is 2.5h-1, reaction temperature is 155 DEG C, TAME conversion ratio 98.5%, and iso-amylene is selective99.8%, methyl alcohol selective 99.5%. 2-methyl-1-butene alkene accounts for iso-amylene (mixing of 2-methyl-2-butene and 2-methyl-1-butene alkeneCompound) ratio 22%.
Embodiment 3
By 30 grams of γ-Al2O3Join in 50ml30% phosphorus molybdenum acid solution and under room temperature, leave standstill 6h, then filter, 100 DEG C dryDry 2h, obtains POMs/Al at 300 DEG C of roasting 8h2O3。
Then Sm (the NO that is 10% by product in 40ml concentration3)3In the aqueous solution, dipping 6h, after filtration, 100 DEG C are dry4h, obtains Sm at 600 DEG C of roasting 1h2O3/POMs/Al2O3。
Again by Sm2O3/POMs/Al2O3Join 100ml concentration and be in 3% hydrofluoric acid solution and flood 1h, filter 100 DEG CDry 4h, at 600 DEG C of roasting 5h, obtains F/Sm of the present invention2O3/POMs/Al2O3。
14g catalyst is packed in the micro fixed-bed reactor of Φ 20mm diameter into tert amyl methyl ether(TAME) micro-amounts of liquidsSampling pump charging, controlling liquid air speed is 2.5h-1, reaction temperature is 155 DEG C, TAME conversion ratio 99.5%, and iso-amylene is selective99.8%, methyl alcohol selective 99.7%. 2-methyl-1-butene alkene accounts for iso-amylene (mixing of 2-methyl-2-butene and 2-methyl-1-butene alkeneCompound) ratio 22%.
Embodiment 4
By 30 grams of γ-Al2O3Join in 50ml15% silicomolybdic acid solution and under room temperature, leave standstill 6h, then filter, 120 DEG C dryDry 4h, obtains POMs/Al at 400 DEG C of roasting 6h2O3。
Then Zr (the NO that is 5% by product in 40ml concentration3)4In the aqueous solution, dipping 6h, after filtration, 100 DEG C of dry 4h,Obtain ZrO at 400 DEG C of roasting 8h2/POMs/Al2O3。
Again by ZrO2/POMs/Al2O3Join 100ml concentration and be in 15% hydrogen chloride solution and flood 3h, filter 120DEG C dry 4h, at 400 DEG C of roasting 5h, obtains Cl/ZrO of the present invention2/POMs/Al2O3。
14g catalyst is packed in the micro fixed-bed reactor of Φ 20mm diameter into tert amyl methyl ether(TAME) micro-amounts of liquidsSampling pump charging, controlling liquid air speed is 2.5h-1, reaction temperature is 160 DEG C, TAME conversion ratio 98.4%, and iso-amylene is selective99.6%, methyl alcohol selective 98.1%. 2-methyl-1-butene alkene accounts for iso-amylene (mixing of 2-methyl-2-butene and 2-methyl-1-butene alkeneCompound) ratio 29%.
Embodiment 5
By 30 grams of γ-Al2O3Join in 50ml30% phosphorus molybdenum acid solution and under room temperature, leave standstill 3h, then filter, 100 DEG C dryDry 4h, obtains POMs/Al at 600 DEG C of roasting 6h2O3。
Then La (the NO that is 5% by product in 40ml concentration3)3In the aqueous solution, dipping 6h, after filtration, 100 DEG C of dry 4h,Obtain La at 600 DEG C of roasting dipping 6h2O3/POMs/Al2O3。
Again by La2O3/POMs/Al2O3Join in 50ml10% hydrogen chloride solution, filter, 100 DEG C of dry 4h, 600DEG C roasting 5h, obtains Cl/La of the present invention2O3/POMs/Al2O3。
14g catalyst is packed in the micro fixed-bed reactor of Φ 20mm diameter into tert amyl methyl ether(TAME) micro-amounts of liquidsSampling pump charging, controlling liquid air speed is 2.5h-1, reaction temperature is 160 DEG C, TAME conversion ratio 99.4%, and iso-amylene is selective99.8%, methyl alcohol selective 99.0%. 2-methyl-1-butene alkene accounts for iso-amylene (mixing of 2-methyl-2-butene and 2-methyl-1-butene alkeneCompound) ratio 26%.
Embodiment 6
By 30 grams of γ-Al2O3Join in 50ml15% silico-tungstic acid solution and under room temperature, leave standstill 6h, then filter, 100 DEG C dryDry 4h, obtains POMs/Al at 400 DEG C of roasting 6h2O3。
Then La (the NO that is 5% by product in 40ml concentration3)3In the aqueous solution, dipping 6h, after filtration, 100 DEG C of dry 4h,Obtain La at 600 DEG C of roasting dipping 6h2O3/POMs/Al2O3。
Again by La2O3/POMs/Al2O3Join 50ml concentration and be in 15% Fluorinse, filter, 100 DEG C dry4h, at 600 DEG C of roasting 5h, obtains F/La of the present invention2O3/POMs/Al2O3。
14g catalyst is packed in the micro fixed-bed reactor of Φ 20mm diameter into tert amyl methyl ether(TAME) micro-amounts of liquidsSampling pump charging, controlling liquid air speed is 2.5h-1, reaction temperature is 160 DEG C, TAME conversion ratio 97.4%, and iso-amylene is selective99.8%, methyl alcohol selective 99.4%. 2-methyl-1-butene alkene accounts for iso-amylene (mixing of 2-methyl-2-butene and 2-methyl-1-butene alkeneCompound) ratio 24%.

Claims (5)

  1. One kind for tert amyl methyl ether(TAME) cracking the X/Z for iso-amylene2O3/POMs/Al2O3Type catalyst, is characterized in thatComponent and percentage by weight are:
    Wherein Al2O3For alundum (Al2O3), derive from hydrated alumina, γ-Al2O3、η-Al2O3Or θ-Al2O3In one;POMs is heteropoly acid and salt thereof, derives from phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, silicotungstic heteropolyacid, silicon-molybdenum heteropoly acid and relevantSalt in one, Z2O3For metal oxide, derive from the one in the aqueous solution salt of Ce, La, Sm and Zr; X is halogen, comesCome from the one in the aqueous solution of ammonium fluoride, sodium fluoride, hydrofluoric acid, ammonium chloride, sodium chloride.
  2. 2. the preparation method of catalyst according to claim 1, its feature is as follows:
    By Al2O3Be immersed in configured containing in the aqueous solution of POMs 1～8 hour, filter, then in 200～800 DEG C of roastingsBurn 2～8 hours, obtain POMs/Al2O3；
    Joined the Z that contains having configured2O3Aqueous solution in flood 1～8 hour, filter, in 80～180 DEG C dry 2～10 hours, then 300～800 DEG C of roastings 2～10 hours, obtained Z2O3/POMs/Al2O3；
    By the Z obtaining2O3/POMs/Al2O3Join in the aqueous solution of halide, filter, dry, 200～800 DEG C of roastings 2～10 hours, obtain the X/Z for the preparation of iso-amylene2O3/POMs/Al2O3Type solid acid catalyst.
  3. 3. the preparation method of catalyst according to claim 2, is characterized in that, it is assorted many that said POMs is selected from phosphorus tungstenOne in acid, phosphato-molybdic heteropolyacid, silicotungstic heteropolyacid, silicon-molybdenum heteropoly acid and relevant salting liquid thereof, the concentration of POMs solution isIn 0.1～50%, POMs solution, the amount of alundum (Al2O3) is 0.1～30g/ml; Metal oxide be selected from metallic element Ce, La,One in the water-soluble salt solution of Sm and Zr, Z2O3The concentration of water-soluble salt solution is 0.01～20%, in aqueous metal saltPOMs/Al2O3Amount be 0.01～30g/ml; X is selected from ammonium fluoride, sodium fluoride, hydrofluoric acid, ammonium chloride, sodium chloride, potassium chlorideOne in the aqueous solution, the concentration of halide solution is 0.01～40%, Z in halide solution2O3/POMs/Al2O3ContainAmount is 0.1～30g/ml.
  4. 4. the application of catalyst claimed in claim 1, reacts reaction temperature for iso-amylene for tert amyl methyl ether(TAME) crackingBe 100～400 DEG C, reaction pressure is 0～2MPa, and liquid air speed is 0.1～20h-1。
  5. 5. the application of catalyst claimed in claim 4, reacts reaction temperature for iso-amylene for tert amyl methyl ether(TAME) crackingBe 120～220 DEG C, reaction pressure is 0～1MPa, and liquid air speed is 0.5～15h-1。
CN201410111268.2A 2014-03-25 2014-03-25 Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene Active CN103846098B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410111268.2A CN103846098B (en) 2014-03-25 2014-03-25 Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410111268.2A CN103846098B (en) 2014-03-25 2014-03-25 Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene

Publications (2)

Publication Number Publication Date
CN103846098A CN103846098A (en) 2014-06-11
CN103846098B true CN103846098B (en) 2016-05-18

Family

ID=50854487

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410111268.2A Active CN103846098B (en) 2014-03-25 2014-03-25 Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene

Country Status (1)

Country Link
CN (1) CN103846098B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104689853B (en) * 2015-03-20 2017-07-28 华东理工大学 A kind of preparation method and application for being used to prepare the catalyst of iso-amylene
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5223464A (en) * 1989-07-31 1993-06-29 Exxon Chemical Patents Inc. Process for regenerating a catalyst used in production of olefins by catalytic ether decomposition
CN1357522A (en) * 2000-12-08 2002-07-10 中国石化集团齐鲁石油化工公司 Process and catalyst for cracking methyl tert-amyl ether to prepare test-amyl olefine
CN103041834A (en) * 2013-01-18 2013-04-17 华东理工大学 Catalyst for preparing isoamylene by splitting decomposition of t-amyl-methyl ether and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5223464A (en) * 1989-07-31 1993-06-29 Exxon Chemical Patents Inc. Process for regenerating a catalyst used in production of olefins by catalytic ether decomposition
CN1357522A (en) * 2000-12-08 2002-07-10 中国石化集团齐鲁石油化工公司 Process and catalyst for cracking methyl tert-amyl ether to prepare test-amyl olefine
CN103041834A (en) * 2013-01-18 2013-04-17 华东理工大学 Catalyst for preparing isoamylene by splitting decomposition of t-amyl-methyl ether and preparation method and application thereof

Also Published As

Publication number Publication date
CN103846098A (en) 2014-06-11

Similar Documents

Publication Publication Date Title
WO2018049735A1 (en) A metal oxide catalyst for methanol synthesis from co2 hydrogenation and preparation method of the catalyst
CN103846098B (en) Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene
CN106563455B (en) Slurry bed system Cu base CO adds hydrogen CH4Catalyst and preparation method and application
CN103041835B (en) Catalyst for preparing high-purity isobutene as well as preparation method and application
CN103041834B (en) Catalyst for preparing isoamylene by splitting decomposition of t-amyl-methyl ether and preparation method and application thereof
CN102503836A (en) Preparation method of dibenzylamine
CN102527411A (en) Catalyst for preparing isoolefin by cracking tertiary alkyl ether, preparation method for catalyst and application of catalyst
CN103831120B (en) For Catalysts and its preparation method and the application of methyl tertiary butyl ether(MTBE) cracking
CN103721709A (en) Preparation method for preparing cyclohexene catalyst by employing selective hydrogenation of benzene
CN104072342A (en) Dehydrogenation method of cyclohexanediol derivatives containing ether bonds
CN104525192A (en) Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene
CN105152842A (en) Reaction system and method for preparing ethylene through acetylene hydrogenation
TWI549749B (en) A catalyst composition for preparing o-phenylphenol and a process for preparing o-phenylphenol using the catalyst composition
CN106366026B (en) A kind of preparation method of sulfhydryl compound
CN100467124C (en) Catalyst for producing isobutene by cracking methyl tert-butyl ether
CN109369366B (en) Method for preparing lactic acid by catalytic dehydrogenation of glycerol
CN112657506A (en) Preparation method of catalyst for preparing isobutanol from synthesis gas
CN100420518C (en) Catalyst of solid acid in use for preparing isobutene, and preparation method
CN103433050A (en) Preparation method of catalyst for synthesizing piperazine through monoethanolamine catalytic amination one-step method
CN104689853B (en) A kind of preparation method and application for being used to prepare the catalyst of iso-amylene
CN103524296B (en) Preparation method of 1,1,2,3-tetrachloropropene
CN106955687B (en) A kind of preparation method and application of the catalyst being used to prepare alkene
CN103480378B (en) The preparation method of Modified Copper-based Catalysts for Methanol
CN101168520B (en) Method for producing 1,1'-phenylsulfonyl-4,4'-diallyl (2) ether
JP2012254447A (en) Catalyst for producing alcohol compound or olefin compound, and method for producing alcohol compound or olefin compound

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant