CN109453822A - One kind is by cracking isobutene by methyl-tert-butyl ether modified silica-gel catalyst for reaction - Google Patents
One kind is by cracking isobutene by methyl-tert-butyl ether modified silica-gel catalyst for reaction Download PDFInfo
- Publication number
- CN109453822A CN109453822A CN201811276795.3A CN201811276795A CN109453822A CN 109453822 A CN109453822 A CN 109453822A CN 201811276795 A CN201811276795 A CN 201811276795A CN 109453822 A CN109453822 A CN 109453822A
- Authority
- CN
- China
- Prior art keywords
- silica gel
- gel
- catalyst
- added
- butyl ether
- 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.)
- Granted
Links
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- BZLVMXJERCGZMT-UHFFFAOYSA-N methyl tert-butyl ether Substances COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 22
- 238000005336 cracking Methods 0.000 title claims abstract description 12
- -1 methyl-tert-butyl ether modified silica-gel Chemical class 0.000 title claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000000741 silica gel Substances 0.000 claims abstract description 56
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 56
- 229960001866 silicon dioxide Drugs 0.000 claims abstract description 56
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005751 Copper oxide Substances 0.000 claims abstract description 12
- 230000004913 activation Effects 0.000 claims abstract description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000010992 reflux Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 9
- 239000004359 castor oil Substances 0.000 claims description 9
- 235000019438 castor oil Nutrition 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000005202 decontamination Methods 0.000 claims description 7
- 230000003588 decontaminative effect Effects 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 108010064470 polyaspartate Proteins 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BRSDPVLOTZLFFV-UHFFFAOYSA-N methanol;2-methylprop-1-ene Chemical compound OC.CC(C)=C BRSDPVLOTZLFFV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HNJLYESLOZWWPL-UHFFFAOYSA-L sodium silicon(4+) carbonate Chemical compound [Si+4].C([O-])([O-])=O.[Na+] HNJLYESLOZWWPL-UHFFFAOYSA-L 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses one kind by cracking isobutene by methyl-tert-butyl ether modified silica-gel catalyst for reaction, is related to catalyst technical field.The preparation method of catalyst of the present invention includes: the activation of silica gel, the modification of silica gel, the load of silica gel；Present invention 'alpha '-hydroxy acids and silane coupling agent are modified processing to silica gel, the activation for utilizing auxiliary agent simultaneously, accelerates the load efficiency of nano-titanium dioxide and copper oxide, while improving positive reaction rate, the progress of side reaction is inhibited, the significant yield and purity for improving isobutene.
Description
Technical field:
The present invention relates to catalyst technical fields, and in particular to a kind of reacted by cracking isobutene by methyl-tert-butyl ether is used
Modified silica-gel catalyst.
Background technique:
Isobutene occupies highly important status in organic chemical industry, fine chemistry industry production, is such as produced by isobutylene oxidation
Methacrylic acid, isobutene is reacted with formaldehyde produces isoamyl olefine aldehydr and isoprene, with 2.6 di-t-butyl of alkylation of phenol system
Phenol, isobutene and isoprene polymerization can obtain butyl rubber, hydration can preparing tert-butanol, isobutene self-polymerization can polyisobutene processed
Deng.The industrial production process of isobutene mainly has: 1. catalytic cracking by-products utilize the molecular sieve systems cracking catalysis such as ZSM-5
The selectivity of agent raising isobutene；2. the technique that fourth burns isomery dehydrogenation again；3. the skeletal isomerization of n-butene；4. tert-butyl alcohol arm water
(mainly from the by-product of propylene and iso-butane cooxidation legal system propylene oxide)；5. methyl tertiary butyl ether(MTBE) is in solid acid catalyst
Act on lower cracking process.A kind of last method is more and more drawn due to the success of the MTBE process of methanol extracting catalytic cracking C 4 fraction
It rises and payes attention to.Main cause is that methyl tertiary butyl ether is readily transported similar to gasoline, and whether the producer for producing isobutene is not had refining by nearby
The limitation of oily factory.And this method is easily obtainable the isobutene of purity is high.
By the process of methyl tertiary butyl ether(MTBE) cracking isobutene it has been reported that such as United States Patent (USP) USP4566016, use
BZSM-5 molecular sieve has applied for the SiO2 system of at least one modification metal of addition in China as catalyst, Compagnie Francise des Petroles
The patent of catalyst, publication number CN1056299A.The reaction that methyl tertiary butyl ether(MTBE) is occurred in weakly acidic oxide catalyst:
Main reaction: methyl tertiary butyl ether(MTBE) → methanol+isobutene
Side reaction: methanol → dimethyl ether+water
Isobutene+water → tert-butyl alcohol
But farthest inhibit the generation of several side reactions, still need further to be solved the problems, such as.Especially first
The dimethyl ether and methyl tertiary butyl ether(MTBE) azeotropic mixture easily generated that one of base tertbutyl ether pyrolysis product methanol dehydration generates, can give subsequent
Separation bring difficulty, increase the cost of product.
Summary of the invention:
Technical problem to be solved by the present invention lies in overcome the deficiencies of the prior art and provide a kind of methyl tertiary butyl ether(MTBE)
The all very high catalyst of the selectivity of conversion ratio and product isobutene.
The following technical solution is employed for the technical problems to be solved by the invention to realize:
The preparation method of modified silica-gel catalyst, comprising the following steps:
(1) activation of silica gel: nitric acid is added in silica gel, is heated to reflux 5h, is washed to neutrality with distillation after cooling, close
Envelope is placed, then with 6N hydrochloric acid in soaking at room temperature for 24 hours, then with distilling neutrality is washed to, then by processed silica gel as muffle furnace
In 120 DEG C of dry 10h, obtain activated silica gel；
(2) modification of silica gel: activated silica gel is added in dehydrated alcohol, is heated to reflux state, insulated and stirred 10-
Then 30min adds 'alpha '-hydroxy acids and silane coupling agent, return stirring 0.5-2h, cooled to room temperature, filtering, gained silicon
Sodium carbonate is added after mixing evenly in glue, is sealed in 0-5 DEG C of standing 0.5-2h to get modified silica-gel is arrived；
(3) load of silica gel: modified silica gel is add to deionized water, be added auxiliary agent, nano-titanium dioxide and
Copper oxide, return stirring 0.5-4h are cooled to 30-35 DEG C of filtering, and obtained solid is sent into 100-110 DEG C of drying box, and drying is extremely
Constant weight to get arrive catalyst.
The silica gel, nitric acid, 'alpha '-hydroxy acids, silane coupling agent, auxiliary agent, nano-titanium dioxide, copper oxide mass ratio be
20-30:20-30:5-10:5-10:1-5:1-3:1-2.
The auxiliary agent the preparation method comprises the following steps: poly-aspartic-acid is add to deionized water, 40 DEG C of stirring 10-20min,
Then polyvinyl alcohol and tetraethyl titanate is added, is heated to reflux state, then castor oil 70- is added in insulated and stirred 0.5-2h
75 DEG C of stirring 30-50min, are filtered while hot, and decontamination is washed with deionized water in obtained solid, and 50 DEG C are dried under vacuum to constant weight.
The poly-aspartic-acid, polyvinyl alcohol, tetraethyl titanate, castor oil mass ratio be 5-10:5-10:00.5-
0.1:1-3.
The molecular weight of the polyvinyl alcohol is 20000-50000, alcoholysis degree 78%.
'alpha '-hydroxy acids can be connected on silica gel with silane coupling agent by chemical bond, improve silica gel to Organic Ingredients
Nano-titanium dioxide, copper oxide are efficiently supported on silica gel by the activation of auxiliary agent by affinity and catalytic activity
On, and then improve the catalytic efficiency of catalyst.The catalyst has the side reaction for producing isobutene simultaneously inhibits to make well
With can significantly improve the yield and purity of isobutene.
Cracking isobutene by methyl-tert-butyl ether reaction is carried out using catalyst of the invention, required reaction temperature is generally
100-180 DEG C, reaction pressure 0-2MPa, optimum response pressure is 0.2-1.0Mpa.The flow velocity of methyl tertiary butyl ether(MTBE), with every small
When per volume of catalyst liquid feed volume (liquid air speed) indicate, generally 0.1-10h-1, optimal liquid air speed is
0.5-6h-1。
The beneficial effects of the present invention are: present invention 'alpha '-hydroxy acids and silane coupling agent are modified processing to silica gel, together
The activation of Shi Liyong auxiliary agent accelerates the load efficiency of nano-titanium dioxide and copper oxide, while improving positive reaction rate,
The progress of side reaction is inhibited, the significant yield and purity for improving isobutene.
Specific embodiment:
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
The preparation of modified silica-gel catalyst:
(1) activation of silica gel: 20 parts of nitric acid are added in 20 parts of silica gel, are heated to reflux 5h, are washed after cooling with distillation
To neutrality, sealing is placed, then with 6N hydrochloric acid in soaking at room temperature for 24 hours, then with distilling be washed to neutrality, then extremely by processed silica gel
120 DEG C of dry 10h, obtain activated silica gel in muffle furnace；
(2) modification of silica gel: activated silica gel is added in dehydrated alcohol, is heated to reflux state, insulated and stirred
Then 30min adds 6 parts of glycolics and 6 parts of silane coupling agents, return stirring 1h, cooled to room temperature, filtering, gained silicon
The sodium carbonate of silica gel quality 5% is added after mixing evenly in glue, is sealed in 3 DEG C of standing 2h to get modified silica-gel is arrived；
(3) load of silica gel: modified silica gel is add to deionized water, and 2 parts of auxiliary agents, 1 part of nano-silica are added
Change titanium and 1 part of copper oxide, return stirring 4h, be cooled to 35 DEG C of filterings, obtained solid is sent into 100-110 DEG C of drying box, dry
To constant weight to get arrive catalyst.
The preparation of auxiliary agent: 6 parts of poly-aspartic-acids are add to deionized water, then 40 DEG C of stirring 10min are added 6
Part polyvinyl alcohol and 00.8 part of tetraethyl titanate, are heated to reflux state, then insulated and stirred 1h is added 2 parts 70 DEG C of castor oil
30min is stirred, is filtered while hot, decontamination is washed with deionized water in obtained solid, and 50 DEG C are dried under vacuum to constant weight.
15 parts of catalyst are fitted into the micro fixed-bed reactor of 20 mm dia of Φ, methyl tertiary butyl ether(MTBE) micro pump
Charging, control liquid air speed are 3h-1,120 DEG C of reaction temperature.
Embodiment 2
The preparation of modified silica-gel catalyst:
(1) activation of silica gel: 25 parts of nitric acid are added in 25 parts of silica gel, are heated to reflux 5h, are washed after cooling with distillation
To neutrality, sealing is placed, then with 6N hydrochloric acid in soaking at room temperature for 24 hours, then with distilling be washed to neutrality, then extremely by processed silica gel
120 DEG C of dry 10h, obtain activated silica gel in muffle furnace；
(2) modification of silica gel: activated silica gel is added in dehydrated alcohol, is heated to reflux state, insulated and stirred
Then 30min adds 6 parts of glycolics and 6 parts of silane coupling agents, return stirring 1h, cooled to room temperature, filtering, gained silicon
The sodium carbonate of silica gel quality 5% is added after mixing evenly in glue, is sealed in 3 DEG C of standing 2h to get modified silica-gel is arrived；
(3) load of silica gel: modified silica gel is add to deionized water, and 2 parts of auxiliary agents, 1 part of nano-silica are added
Change titanium and 1 part of copper oxide, return stirring 4h, be cooled to 35 DEG C of filterings, obtained solid is sent into 100-110 DEG C of drying box, dry
To constant weight to get arrive catalyst.
The preparation of auxiliary agent: 6 parts of poly-aspartic-acids are add to deionized water, then 40 DEG C of stirring 10min are added 6
Part polyvinyl alcohol and 00.8 part of tetraethyl titanate, are heated to reflux state, then insulated and stirred 1h is added 2 parts 70 DEG C of castor oil
30min is stirred, is filtered while hot, decontamination is washed with deionized water in obtained solid, and 50 DEG C are dried under vacuum to constant weight.
15 parts of catalyst are fitted into the micro fixed-bed reactor of 20 mm dia of Φ, methyl tertiary butyl ether(MTBE) micro pump
Charging, control liquid air speed are 5h-1,150 DEG C of reaction temperature.
Reference examples 1
The preparation of modified silica-gel catalyst:
(1) activation of silica gel: 20 parts of nitric acid are added in 20 parts of silica gel, are heated to reflux 5h, are washed after cooling with distillation
To neutrality, sealing is placed, then with 6N hydrochloric acid in soaking at room temperature for 24 hours, then with distilling be washed to neutrality, then extremely by processed silica gel
120 DEG C of dry 10h, obtain activated silica gel in muffle furnace；
(2) modification of silica gel: activated silica gel is added in dehydrated alcohol, is heated to reflux state, insulated and stirred
Then 30min adds 6 parts of silane coupling agents, return stirring 1h, cooled to room temperature, filtering, silica obtained addition silica gel matter
The sodium carbonate of amount 5% after mixing evenly, is sealed in 3 DEG C of standing 2h to get modified silica-gel is arrived；
(3) load of silica gel: modified silica gel is add to deionized water, and 2 parts of auxiliary agents, 1 part of nano-silica are added
Change titanium and 1 part of copper oxide, return stirring 4h, be cooled to 35 DEG C of filterings, obtained solid is sent into 100-110 DEG C of drying box, dry
To constant weight to get arrive catalyst.
The preparation of auxiliary agent: 6 parts of poly-aspartic-acids are add to deionized water, then 40 DEG C of stirring 10min are added 6
Part polyvinyl alcohol and 00.8 part of tetraethyl titanate, are heated to reflux state, then insulated and stirred 1h is added 2 parts 70 DEG C of castor oil
30min is stirred, is filtered while hot, decontamination is washed with deionized water in obtained solid, and 50 DEG C are dried under vacuum to constant weight.
15 parts of catalyst are fitted into the micro fixed-bed reactor of 20 mm dia of Φ, methyl tertiary butyl ether(MTBE) micro pump
Charging, control liquid air speed are 3h-1,120 DEG C of reaction temperature.
Reference examples 2
The preparation of modified silica-gel catalyst:
(1) activation of silica gel: 20 parts of nitric acid are added in 20 parts of silica gel, are heated to reflux 5h, are washed after cooling with distillation
To neutrality, sealing is placed, then with 6N hydrochloric acid in soaking at room temperature for 24 hours, then with distilling be washed to neutrality, then extremely by processed silica gel
120 DEG C of dry 10h, obtain activated silica gel in muffle furnace；
(2) modification of silica gel: activated silica gel is added in dehydrated alcohol, is heated to reflux state, insulated and stirred
Then 30min adds 6 parts of glycolics, return stirring 1h, cooled to room temperature, filtering, silica obtained addition silica gel quality
5% sodium carbonate after mixing evenly, is sealed in 3 DEG C of standing 2h to get modified silica-gel is arrived；
(3) load of silica gel: modified silica gel is add to deionized water, and 2 parts of auxiliary agents, 1 part of nano-silica are added
Change titanium and 1 part of copper oxide, return stirring 4h, be cooled to 35 DEG C of filterings, obtained solid is sent into 100-110 DEG C of drying box, dry
To constant weight to get arrive catalyst.
The preparation of auxiliary agent: 6 parts of poly-aspartic-acids are add to deionized water, then 40 DEG C of stirring 10min are added 6
Part polyvinyl alcohol and 00.8 part of tetraethyl titanate, are heated to reflux state, then insulated and stirred 1h is added 2 parts 70 DEG C of castor oil
30min is stirred, is filtered while hot, decontamination is washed with deionized water in obtained solid, and 50 DEG C are dried under vacuum to constant weight.
15 parts of catalyst are fitted into the micro fixed-bed reactor of 20 mm dia of Φ, methyl tertiary butyl ether(MTBE) micro pump
Charging, control liquid air speed are 3h-1,120 DEG C of reaction temperature.
Reference examples 3
The preparation of modified silica-gel catalyst:
(1) activation of silica gel: 20 parts of nitric acid are added in 20 parts of silica gel, are heated to reflux 5h, are washed after cooling with distillation
To neutrality, sealing is placed, then with 6N hydrochloric acid in soaking at room temperature for 24 hours, then with distilling be washed to neutrality, then extremely by processed silica gel
120 DEG C of dry 10h, obtain activated silica gel in muffle furnace；
(2) modification of silica gel: activated silica gel is added in dehydrated alcohol, is heated to reflux state, insulated and stirred
Then 30min adds 6 parts of glycolics and 6 parts of silane coupling agents, return stirring 1h, cooled to room temperature, filtering, gained silicon
The sodium carbonate of silica gel quality 5% is added after mixing evenly in glue, is sealed in 3 DEG C of standing 2h to get modified silica-gel is arrived；
(3) load of silica gel: modified silica gel is add to deionized water, and 2 parts of auxiliary agents, 1 part of nano-silica are added
Change titanium and 1 part of copper oxide, return stirring 4h, be cooled to 35 DEG C of filterings, obtained solid is sent into 100-110 DEG C of drying box, dry
To constant weight to get arrive catalyst.
The preparation of auxiliary agent: 6 parts of poly-aspartic-acids are add to deionized water, then 40 DEG C of stirring 10min are added 6
Part polyvinyl alcohol and 00.8 part of tetraethyl titanate, are heated to reflux state, insulated and stirred 1h, then 70 DEG C of stirring 30min, while hot
Decontamination is washed with deionized water in filtering, obtained solid, and 50 DEG C are dried under vacuum to constant weight.
15 parts of catalyst are fitted into the micro fixed-bed reactor of 20 mm dia of Φ, methyl tertiary butyl ether(MTBE) micro pump
Charging, control liquid air speed are 3h-1,120 DEG C of reaction temperature.
Reference examples 4
The preparation of modified silica-gel catalyst:
(1) activation of silica gel: 20 parts of nitric acid are added in 20 parts of silica gel, are heated to reflux 5h, are washed after cooling with distillation
To neutrality, sealing is placed, then with 6N hydrochloric acid in soaking at room temperature for 24 hours, then with distilling be washed to neutrality, then extremely by processed silica gel
120 DEG C of dry 10h, obtain activated silica gel in muffle furnace；
(2) modification of silica gel: activated silica gel is added in dehydrated alcohol, is heated to reflux state, insulated and stirred
Then 30min adds 6 parts of glycolics and 6 parts of silane coupling agents, return stirring 1h, cooled to room temperature, filtering, gained silicon
The sodium carbonate of silica gel quality 5% is added after mixing evenly in glue, is sealed in 3 DEG C of standing 2h to get modified silica-gel is arrived；
(3) load of silica gel: modified silica gel is add to deionized water, and 1 part of nano-titanium dioxide and 1 part is added
Copper oxide, return stirring 4h are cooled to 35 DEG C of filterings, and obtained solid is sent into 100-110 DEG C of drying box, drying to constant weight, i.e.,
Obtain catalyst.
15 parts of catalyst are fitted into the micro fixed-bed reactor of 20 mm dia of Φ, methyl tertiary butyl ether(MTBE) micro pump
Charging, control liquid air speed are 3h-1,120 DEG C of reaction temperature.
Embodiment 3
Based on embodiment 1, setting do not add the reference examples 1 of glycolic, the reference examples 2 for not adding silane coupling agent,
The reference examples 3 of castor oil are not added, do not add the reference examples 4 of auxiliary agent.
The preparation of isobutene is carried out using embodiment 1-2, reference examples 1-4, and related data is detected, as a result such as table
Shown in 1.
The correlated performance detection of 1 isobutene of table
| Test item | Methyl tertiary butyl ether(MTBE) conversion ratio | Selective isobutene | Methanol selectivity |
| Embodiment 1 | 99.5% | 99.6% | 99.1% |
| Embodiment 2 | 99.6% | 99.4% | 99.5% |
| Reference examples 1 | 96.8% | 94.6% | 94.2% |
| Reference examples 2 | 97.1% | 95.1% | 93.3% |
| Reference examples 3 | 98.2% | 90.3% | 91.2% |
| Reference examples 4 | 87.5% | 86.8% | 84.5% |
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (4)
1. one kind is by cracking isobutene by methyl-tert-butyl ether modified silica-gel catalyst for reaction, which is characterized in that modified silica-gel
The preparation method of catalyst, comprising the following steps:
(1) activation of silica gel: nitric acid is added in silica gel, is heated to reflux 5h, is washed to neutrality with distillation after cooling, sealing is put
Set, then with 6N hydrochloric acid in soaking at room temperature for 24 hours, then with distillation neutrality is washed to, then by processed silica gel as in muffle furnace 120
DEG C dry 10h, obtains activated silica gel；
(2) modification of silica gel: activated silica gel is added in dehydrated alcohol, is heated to reflux state, insulated and stirred 10-30min,
Then 'alpha '-hydroxy acids and silane coupling agent, return stirring 0.5-2h, cooled to room temperature, filtering, silica obtained addition are added
Sodium carbonate after mixing evenly, is sealed in 0-5 DEG C of standing 0.5-2h to get modified silica-gel is arrived；
(3) load of silica gel: modified silica gel is add to deionized water, and auxiliary agent, nano-titanium dioxide and oxidation is added
Copper, return stirring 0.5-4h are cooled to 30-35 DEG C of filtering, and obtained solid is sent into 100-110 DEG C of drying box, drying to constant weight,
Obtain catalyst.
2. it is according to claim 1 by cracking isobutene by methyl-tert-butyl ether modified silica-gel catalyst for reaction, it is special
Sign is: the silica gel, nitric acid, 'alpha '-hydroxy acids, silane coupling agent, auxiliary agent, nano-titanium dioxide, copper oxide mass ratio be
20-30:20-30:5-10:5-10:1-5:1-3:1-2.
3. it is according to claim 1 by cracking isobutene by methyl-tert-butyl ether modified silica-gel catalyst for reaction, it is special
Sign is, the auxiliary agent the preparation method comprises the following steps: poly-aspartic-acid is add to deionized water, 40 DEG C of stirring 10-20min,
Then polyvinyl alcohol and tetraethyl titanate is added, is heated to reflux state, then castor oil 70- is added in insulated and stirred 0.5-2h
75 DEG C of stirring 30-50min, are filtered while hot, and decontamination is washed with deionized water in obtained solid, and 50 DEG C are dried under vacuum to constant weight.
4. it is according to claim 3 by cracking isobutene by methyl-tert-butyl ether modified silica-gel catalyst for reaction, it is special
Sign is: the poly-aspartic-acid, polyvinyl alcohol, tetraethyl titanate, castor oil mass ratio be 5-10:5-10:00.5-
0.1:1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811276795.3A CN109453822B (en) | 2018-10-30 | 2018-10-30 | Modified silica gel catalyst for reaction of preparing isobutene by cracking methyl tert-butyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811276795.3A CN109453822B (en) | 2018-10-30 | 2018-10-30 | Modified silica gel catalyst for reaction of preparing isobutene by cracking methyl tert-butyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109453822A true CN109453822A (en) | 2019-03-12 |
| CN109453822B CN109453822B (en) | 2021-06-08 |
Family
ID=65608838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811276795.3A Active CN109453822B (en) | 2018-10-30 | 2018-10-30 | Modified silica gel catalyst for reaction of preparing isobutene by cracking methyl tert-butyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109453822B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056299A (en) * | 1990-04-09 | 1991-11-20 | 法国石油公司 | The method for preparing at least a tertiary olefin by the decomposition of corresponding ether |
| CN101444735A (en) * | 2008-12-19 | 2009-06-03 | 上海工程技术大学 | Ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen and preparation method and application thereof |
| WO2013060262A1 (en) * | 2011-10-25 | 2013-05-02 | 中国石油化工股份有限公司 | Isobutene catalyst prepared by splitting methyl tert-butyl ether, preparation method and use thereof |
| CN103521186A (en) * | 2013-09-27 | 2014-01-22 | 湖南中烟工业有限责任公司 | Silica gel with ionic liquid and mercaptan loaded on surface as well as preparation method and application |
| US9963651B1 (en) * | 2009-07-29 | 2018-05-08 | The United States Of America As Represented By The Secretary Of The Navy | High density cyclic fuels derived from linear sesquiterpenes |
-
2018
- 2018-10-30 CN CN201811276795.3A patent/CN109453822B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056299A (en) * | 1990-04-09 | 1991-11-20 | 法国石油公司 | The method for preparing at least a tertiary olefin by the decomposition of corresponding ether |
| CN101444735A (en) * | 2008-12-19 | 2009-06-03 | 上海工程技术大学 | Ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen and preparation method and application thereof |
| US9963651B1 (en) * | 2009-07-29 | 2018-05-08 | The United States Of America As Represented By The Secretary Of The Navy | High density cyclic fuels derived from linear sesquiterpenes |
| WO2013060262A1 (en) * | 2011-10-25 | 2013-05-02 | 中国石油化工股份有限公司 | Isobutene catalyst prepared by splitting methyl tert-butyl ether, preparation method and use thereof |
| CN103521186A (en) * | 2013-09-27 | 2014-01-22 | 湖南中烟工业有限责任公司 | Silica gel with ionic liquid and mercaptan loaded on surface as well as preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109453822B (en) | 2021-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105330836B (en) | A kind of synthetic method of epoxy terminated allyl alcohol polyethenoxy ether | |
| CN101343260A (en) | Method for synthesis epoxy cyclohexane with titanium molecular sieve catalysis | |
| CN103360215A (en) | Method for synthesizing isopentenol from 3-methyl-3-butene-1-ol through catalytic transposition in water-organic two-phase system | |
| CN101069858A (en) | Method for recovering aluminium alcoholate catalyst in preparation of non-saturated alcohol by transfer reduction of non-saturated aldehydo-hydrogen | |
| CN109453822A (en) | One kind is by cracking isobutene by methyl-tert-butyl ether modified silica-gel catalyst for reaction | |
| CN109603907B (en) | Preparation method of glycollic acid by catalytic hydrolysis of methyl glycolate | |
| CN102167657B (en) | Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst | |
| CN108786846B (en) | Zirconium silicate modified sulfonic acid grafted mesoporous silica catalyst, and preparation method and application thereof | |
| CN103508885B (en) | One utilizes C after ether 4cut prepares the method for 2-butyl acetate | |
| CN102757341A (en) | Preparation method of ethyl acetate and/or isopropyl acetate | |
| CN1432431A (en) | Catalyst for cracking ether to prepare tert-olefine and its prepn and application | |
| CN105712830B (en) | A kind of preparation method of isobutene | |
| CN109225349B (en) | Preparation method of catalyst for preparing isobutene by cracking methyl tert-butyl ether | |
| CN101391942B (en) | Process for preparing citral | |
| CN105712818B (en) | A kind of method that MTBE and TBA compounds prepare isobutene | |
| EP1071649B1 (en) | Tertiary alkyl ester preparation | |
| US6242640B1 (en) | Tertiary alkyl ester preparation using large-pore zeolite catalysts | |
| CN107952479B (en) | Functionalized polyacid ionic liquid catalyst, preparation method and method for catalyzing direct esterification of cyclohexene by functionalized polyacid ionic liquid catalyst | |
| CN103787877B (en) | Preparation method of cyclohexyl acetate | |
| US3979465A (en) | Process for the production of lower aliphatic alcohols | |
| CN106946675A (en) | The new technology and its solid catalyst of acetaldehyde one-step synthesis method crotonaldehyde | |
| CN106669683B (en) | A kind of hud typed amorphous silicon Al catalysts and its preparation method and application | |
| CN106673948B (en) | The method that MTBE and TBA mixture prepares isobutene | |
| CN105709715B (en) | It is a kind of to be used to prepare catalyst of isobutene and preparation method thereof | |
| CN105712831B (en) | A kind of method of methyl tertiary butyl ether(MTBE) and the tert-butyl alcohol compound preparing isobutene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210402 Address after: Room 13002, Bengbu International Plaza, Huaiyuan City, Anhui Province Applicant after: Bengbu Zhibo Automation Technology Development Co.,Ltd. Address before: 238200 Fine Chemical Base of Wujiang Town, Ma'anshan City and County, Anhui Province Applicant before: ANHUI HAIDE CHEMICAL TECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211124 Address after: 238200 Fine Chemical Base of Wujiang Town, Ma'anshan City and County, Anhui Province Patentee after: ANHUI HAIDE CHEMICAL TECHNOLOGY Co.,Ltd. Address before: Room 13002, Bengbu International Plaza, Huaiyuan City, Anhui Province Patentee before: Bengbu Zhibo Automation Technology Development Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240201 Address after: 243000 No.1 Chaosan Road, Provincial Fine Chemical Base, Hexian Economic Development Zone, Ma'anshan City, Anhui Province Patentee after: Anhui Jubaoshi Technology Co.,Ltd. Country or region after: China Address before: 238200 Fine Chemical Base of Wujiang Town, Ma'anshan City and County, Anhui Province Patentee before: ANHUI HAIDE CHEMICAL TECHNOLOGY Co.,Ltd. Country or region before: China |