CN106966878A - The method that the bivalve layer molecular sieve catalytic dehydrating glycerins of ZSM 5 prepare methacrylaldehyde - Google Patents
The method that the bivalve layer molecular sieve catalytic dehydrating glycerins of ZSM 5 prepare methacrylaldehyde Download PDFInfo
- Publication number
- CN106966878A CN106966878A CN201710240117.0A CN201710240117A CN106966878A CN 106966878 A CN106966878 A CN 106966878A CN 201710240117 A CN201710240117 A CN 201710240117A CN 106966878 A CN106966878 A CN 106966878A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zsm
- bivalve
- catalyst
- methacrylaldehyde
- 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.)
- Withdrawn
Links
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- 150000002314 glycerols Chemical class 0.000 title abstract 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 14
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010931 ester hydrolysis Methods 0.000 claims description 7
- 238000004817 gas chromatography Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 238000004451 qualitative analysis Methods 0.000 claims description 7
- 238000004445 quantitative analysis Methods 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 3
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- OKUSWAGOKUGEDX-UHFFFAOYSA-N C(CCC)Br(CCCC)(CCCC)CCCC Chemical compound C(CCC)Br(CCCC)(CCCC)CCCC OKUSWAGOKUGEDX-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000003225 biodiesel Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000002242 deionisation method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B01J35/615—
-
- B01J35/617—
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the method that a kind of bivalve layer molecular sieve catalytic dehydrating glycerins of ZSM 5 prepare methacrylaldehyde, comprise the following steps：ZSM molecular sieves are prepared first, then the molecular sieves of ZSM 5 of preparation are mixed evenly with alkaline substance solution, the stirring reaction at 80 200 DEG C, centrifuge washing after the completion of reaction, are dried, and the bivalve layer molecular sieves of ZSM 5 are made in roasting；Finally under the catalysis of the bivalve layer molecular sieves of ZSM 5, methacrylaldehyde is made in dehydrating glycerin.Layer ZSM 5 molecular sieve catalytic active centers in bivalve produced by the present invention are more, in chemical reaction, and the resistance to mass tranfer that molecule diffusion is subject to is small, so as to effectively increase the conversion ratio of glycerine, the selectivity of products collection efficiency and methacrylaldehyde is also effectively improved.
Description
Technical field：
The present invention relates to organic synthesis field, it is specifically related to bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst and prepares third
The method of olefine aldehydr.
Background technology：
In recent years, as global energy is in short supply, environmental pollution the problems such as be on the rise, national governments are all actively seeking clear
Clean regenerative resource and green chemical industry production technology.Biodiesel is a kind of environmental protection and the good cleaning renewable energy of security
Source, is widely paid attention to and fast-developing in some countries, European Union planned 2015 by biodiesel in business
The ratio of fuel brings up to 10%, while the U.S., Australia, Japan and other countries also provide the time in restriction with legal form
Application of the biodiesel in transportation fuel was set to exceed certain ratio in the past.With the production scale and production capacity of biodiesel
Increase year by year, the trans-utilization of its Main By product crude glycerine turns into a urgent problem to be solved.
Biodiesel accessory substance crude glycerine value it is not high, but the polyfunctional group structure and performance of itself allow its from
Different response paths produces the chemicals of high added value, such as methacrylaldehyde, pyruvic alcohol, 1,3-PD, lactic acid and dihydroxy third
The products such as ketone.Methacrylaldehyde is a kind of simplest unsaturated aldehyde, and its chemical property is active, is in the middle of a kind of important organic chemical industry
Body, has in terms of pharmaceutical synthesis, coating, papermaking, oil field, organic synthesis industry and has been widely used.While the easy oxygen of methacrylaldehyde
Turn to the acrylic acid that market capacity is big and added value is high.The crude glycerine catalysis of biodiesel byproduct is made full use of to prepare methacrylaldehyde,
Both the comprehensive utilization ratio of resource can be improved, more can extend Biodiesel chain, the entirety for improving biodiesel pollution-free industry is competing
Power is striven, is had broad application prospects.
Catalyst is that glycerine high selectivity produces one of key factor of methacrylaldehyde.Molecular sieve has unique hole knot because of it
Structure, suitable acid and good hydrothermal stability turn into catalyst important in modern chemical industry.Molecular sieve have compared with
Good performance, but to be influenceed in the reaction by mass transfer, acidic zeolite and heat endurance, influence molecule diffusion, so that
Influence its catalytic activity.
Periodical " glycerine gas-phase dehydration prepares methacrylaldehyde on Phosphorous Modified HZSM-5 ", Gu Yun is of heap of stone etc., on 02 10th, 2011 " it is public
Open and used the HSZM-5 of phosphoric acid modification to be applied to dehydrating glycerin reaction system, phosphoric acid modification for the preformed catalyst of active component
Afterwards, although acid strength is big, and reactivity is improved a lot, but with the progress of reaction, starting stage glycerol molecule is easy to
The condensation generation coke on acidity of catalyst position, so that the acidic site of covering catalyst, the duct of blocking catalyst, so as to influence
The conversion ratio of glycerine.
The content of the invention：
In order to solve the deficiencies in the prior art, the invention provides a kind of bivalve layer ZSM-5 molecular sieve, it is by two layers of isomorphous
Type molecular sieve is constituted, and cavity structure is also formed between shell, and catalytic activity is high, and heat endurance is good, effectively increases the conversion of glycerine
Rate.
In order to preferably solve the above problems, the present invention uses following technical scheme：
The method that bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst prepares methacrylaldehyde, comprises the following steps：
(1) added after deionized water, mass fraction being mixed evenly for the 40% TPAOH aqueous solution
NaAlO2, continues stirring and obtains mixed solution；Tetraethyl orthosilicate is added dropwise into mixed solution, stirring makes positive silicic acid tetrem
Crystallization 3 days, centrifuge washing, drying, roasting at 170 DEG C, are made ZSM-5 molecular sieve after ester hydrolysis is complete；
(2) ZSM-5 molecular sieve is mixed evenly with alkaline substance solution, then heats to 80-200 DEG C, continuation
Stirring reaction 5-200h, after the completion of reaction, centrifuge washing is dried, roasting, obtains bivalve layer ZSM-5 molecular sieve；
(3) bivalve obtained above layer ZSM-5 molecular sieve is fixed on to the stage casing of micro fixed-bed reactor, glycerine is passed through
Before the aqueous solution, it is passed through at 270-300 DEG C after nitrogen purging catalyst 20-30min, glycerine water solution is injected by syringe pump
Into reactor, with bivalve layer ZSM-5 molecular sieve haptoreaction after gasifying through helical groove, after mixture of reaction products is condensed
Take in collector, timing sampling carries out qualitative and quantitative analysis through gas-chromatography.
As the preferred of above-mentioned technical proposal, in step (1), the deionized water, the TPAOH aqueous solution,
NaAlO2, the mass ratio of tetraethyl orthosilicate are：(10.05-10.40)g：(9.12-9.17)g：(0.325-0.328)g：
(20.80-20.85)g。
As the preferred of above-mentioned technical proposal, in step (2), the alkaline matter is the mixing of quaternary ammonium salt and sodium hydroxide
Thing, the two mol ratio is 1:1.
As the preferred of above-mentioned technical proposal, in step (2), the alkaline matter is the mixing of quaternary ammonium salt and potassium hydroxide
Thing, the two mol ratio is 1:1.
As the preferred of above-mentioned technical proposal, in step (2), the alkaline matter is one kind in n-butylamine, quaternary ammonium base
Or two kinds of mixing.
As the preferred of above-mentioned technical proposal, in step (2), the quaternary ammonium salt is 4 bromide, tetraethyl bromination
One or more in ammonium, 4-propyl bromide and TBAB.
As the preferred of above-mentioned technical proposal, the quaternary ammonium base is TMAH, tetraethyl ammonium hydroxide and four
One or more in butyl ammonium hydroxide.
As the preferred of above-mentioned technical proposal, in step (2), the sintering temperature is 500-900 DEG C, and roasting time is 1-
12h。
As the preferred of above-mentioned technical proposal, in step (3), the mass concentration of the glycerine water solution is 10-20%.
As the preferred of above-mentioned technical proposal, in step (3), the speed that the glycerine water solution is injected into reactor is
5-15ml/min。
The invention has the advantages that：
ZSM-5 molecular sieve is made in the present invention first, and the ZSM- molecules of bivalve layer are then prepared using a step crystallization method
Sieve, its shell is made up of two layers of isomorphism molecular sieve, and cavity structure is formed between shell, and its external diameter is 50nm-5 μm, specific surface area
For 200-1000m2/ g, catalytic active center is more, and heat endurance is good, when being reacted for glycerin catalytic, the biography that molecule diffusion is subject to
Matter resistance is small, and product yield and selectivity all effectively improve.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
The method that bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst prepares methacrylaldehyde, comprises the following steps：
(1) added after deionized water, mass fraction being mixed evenly for the 40% TPAOH aqueous solution
NaAlO2, continues stirring and obtains mixed solution；Tetraethyl orthosilicate is added dropwise into mixed solution, stirring makes positive silicic acid tetrem
Crystallization 3 days, centrifuge washing, drying, roasting at 170 DEG C, are made ZSM-5 molecular sieve after ester hydrolysis is complete；Wherein, deionization
Water, the TPAOH aqueous solution, NaAlO2, the mass ratio of tetraethyl orthosilicate are：10.05g：9.12g：0.325g：
20.80g；
(2) ZSM-5 molecular sieve is mixed evenly with alkaline substance solution, then heats to 80 DEG C, continue to stir
200h is reacted, after the completion of reaction, centrifuge washing is dried, 500 DEG C of roasting 12h obtain bivalve layer ZSM-5 molecular sieve；Wherein, alkali
Property material be 4 bromide and sodium hydroxide mixture, the two mol ratio is 1:1；
(3) bivalve obtained above layer ZSM-5 molecular sieve is fixed on to the stage casing of micro fixed-bed reactor, 10% is passed through
Glycerine water solution before, be passed through at 270 DEG C after nitrogen purging catalyst 20min, by glycerine water solution with 5ml/min speed
Degree is injected into reactor by syringe pump, with bivalve layer ZSM-5 molecular sieve haptoreaction, reaction product after gasifying through helical groove
After mixture is condensed in income collector, timing sampling carries out qualitative and quantitative analysis through gas-chromatography.
Through analysis, react after 20h, glycerol conversion yield is 98.5%, methacrylaldehyde yield is 96.0%, the selectivity of methacrylaldehyde
For 97.5%.
Embodiment 2
The method that bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst prepares methacrylaldehyde, comprises the following steps：
(1) added after deionized water, mass fraction being mixed evenly for the 40% TPAOH aqueous solution
NaAlO2, continues stirring and obtains mixed solution；Tetraethyl orthosilicate is added dropwise into mixed solution, stirring makes positive silicic acid tetrem
Crystallization 3 days, centrifuge washing, drying, roasting at 170 DEG C, are made ZSM-5 molecular sieve after ester hydrolysis is complete；Wherein, deionization
Water, the TPAOH aqueous solution, NaAlO2, the mass ratio of tetraethyl orthosilicate are：10.40g：9.17g：0.328g：
20.85g；
(2) ZSM-5 molecular sieve is mixed evenly with alkaline substance solution, then heats to 200 DEG C, continue to stir
5h is reacted, after the completion of reaction, centrifuge washing is dried, 900 DEG C of roasting 1h obtain bivalve layer ZSM-5 molecular sieve；Wherein, basic species
Matter is the mixture of tetraethylammonium bromide and potassium hydroxide, and the two mol ratio is 1:1；
(3) bivalve obtained above layer ZSM-5 molecular sieve is fixed on to the stage casing of micro fixed-bed reactor, 20% is passed through
Glycerine water solution before, be passed through at 300 DEG C after nitrogen purging catalyst 30min, by glycerine water solution with 15ml/min's
Speed is injected into reactor by syringe pump, with bivalve layer ZSM-5 molecular sieve haptoreaction, reaction production after gasifying through helical groove
After thing mixture is condensed in income collector, timing sampling carries out qualitative and quantitative analysis through gas-chromatography.
Through analysis, react after 20h, glycerol conversion yield is 99.6%, methacrylaldehyde yield is 96.0%, the selectivity of methacrylaldehyde
For 96.4%.
Embodiment 3
The method that bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst prepares methacrylaldehyde, comprises the following steps：
(1) added after deionized water, mass fraction being mixed evenly for the 40% TPAOH aqueous solution
NaAlO2, continues stirring and obtains mixed solution；Tetraethyl orthosilicate is added dropwise into mixed solution, stirring makes positive silicic acid tetrem
Crystallization 3 days, centrifuge washing, drying, roasting at 170 DEG C, are made ZSM-5 molecular sieve after ester hydrolysis is complete；Wherein, deionization
Water, the TPAOH aqueous solution, NaAlO2, the mass ratio of tetraethyl orthosilicate are：10.15g：9.13g：0.326g：
20.82g；
(2) ZSM-5 molecular sieve is mixed evenly with alkaline substance solution, then heats to 100 DEG C, continue to stir
50h is reacted, after the completion of reaction, centrifuge washing is dried, 600 DEG C of roasting 5h obtain bivalve layer ZSM-5 molecular sieve；Wherein, it is alkaline
Material is TMAH；
(3) bivalve obtained above layer ZSM-5 molecular sieve is fixed on to the stage casing of micro fixed-bed reactor, 15% is passed through
Glycerine water solution before, be passed through at 270 DEG C after nitrogen purging catalyst 30min, by glycerine water solution with 7ml/min speed
Degree is injected into reactor by syringe pump, with bivalve layer ZSM-5 molecular sieve haptoreaction, reaction product after gasifying through helical groove
After mixture is condensed in income collector, timing sampling carries out qualitative and quantitative analysis through gas-chromatography.
Through analysis, react after 20h, glycerol conversion yield is 98.8%, methacrylaldehyde yield is 96.5%, the selectivity of methacrylaldehyde
For 97.7%.
Embodiment 4
The method that bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst prepares methacrylaldehyde, comprises the following steps：
(1) added after deionized water, mass fraction being mixed evenly for the 40% TPAOH aqueous solution
NaAlO2, continues stirring and obtains mixed solution；Tetraethyl orthosilicate is added dropwise into mixed solution, stirring makes positive silicic acid tetrem
Crystallization 3 days, centrifuge washing, drying, roasting at 170 DEG C, are made ZSM-5 molecular sieve after ester hydrolysis is complete；Wherein, deionization
Water, the TPAOH aqueous solution, NaAlO2, the mass ratio of tetraethyl orthosilicate are：10.25g：9.14g：0.327g：
20.83g；
(2) ZSM-5 molecular sieve is mixed evenly with alkaline substance solution, then heats to 130 DEG C, continue to stir
120h is reacted, after the completion of reaction, centrifuge washing is dried, 700 DEG C of roasting 10h obtain bivalve layer ZSM-5 molecular sieve；Wherein, alkali
Property material be tetraethyl ammonium hydroxide；
(3) bivalve obtained above layer ZSM-5 molecular sieve is fixed on to the stage casing of micro fixed-bed reactor, 15% is passed through
Glycerine water solution before, be passed through at 290 DEG C after nitrogen purging catalyst 20min, by glycerine water solution with 9ml/min speed
Degree is injected into reactor by syringe pump, with bivalve layer ZSM-5 molecular sieve haptoreaction, reaction product after gasifying through helical groove
After mixture is condensed in income collector, timing sampling carries out qualitative and quantitative analysis through gas-chromatography.
Through analysis, react after 20h, glycerol conversion yield is 98.5%, methacrylaldehyde yield is 96.0%, the selectivity of methacrylaldehyde
For 99.5%.
Embodiment 5
The method that bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst prepares methacrylaldehyde, comprises the following steps：
(1) added after deionized water, mass fraction being mixed evenly for the 40% TPAOH aqueous solution
NaAlO2, continues stirring and obtains mixed solution；Tetraethyl orthosilicate is added dropwise into mixed solution, stirring makes positive silicic acid tetrem
Crystallization 3 days, centrifuge washing, drying, roasting at 170 DEG C, are made ZSM-5 molecular sieve after ester hydrolysis is complete；Wherein, deionization
Water, the TPAOH aqueous solution, NaAlO2, the mass ratio of tetraethyl orthosilicate are：10.35g：9.15g：0.327g：
20.84g；
(2) ZSM-5 molecular sieve is mixed evenly with alkaline substance solution, then heats to 180 DEG C, continue to stir
100h is reacted, after the completion of reaction, centrifuge washing is dried, 850 DEG C of roasting 5h obtain bivalve layer ZSM-5 molecular sieve；Wherein, it is alkaline
Material is n-butylamine；
(3) bivalve obtained above layer ZSM-5 molecular sieve is fixed on to the stage casing of micro fixed-bed reactor, 15% is passed through
Glycerine water solution before, be passed through at 290 DEG C after nitrogen purging catalyst 30min, by glycerine water solution with 12ml/min's
Speed is injected into reactor by syringe pump, with bivalve layer ZSM-5 molecular sieve haptoreaction, reaction production after gasifying through helical groove
After thing mixture is condensed in income collector, timing sampling carries out qualitative and quantitative analysis through gas-chromatography.
Through analysis, react after 20h, glycerol conversion yield is 99.3%, methacrylaldehyde yield is 97.5%, the selectivity of methacrylaldehyde
For 98.2%.
Comparative example 1
Catalyst uses simple ZSM-5 molecular sieve, is handled without bivalve stratification, other reaction conditions and embodiment 5
It is identical.
Through analysis, glycerol conversion yield is 86.3%, and the yield of methacrylaldehyde is 62.8%, and the selectivity of methacrylaldehyde is
72.8%, but the catalyst is just inactivated after reaction 15h.
Comparative example 2
Catalyst uses the ZSM-5 molecular sieve of monoshell Rotating fields, and other reaction conditions and embodiment 5 are identical.
Through analysis, glycerol conversion yield is 90.5%, and the yield of methacrylaldehyde is 73.6%, and the selectivity of methacrylaldehyde is
81.3%.Inactivated after catalyst reaction 20h.
Claims (10)
1. the method that bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst prepares methacrylaldehyde, it is characterised in that comprise the following steps：
(1) added after deionized water, mass fraction being mixed evenly for the 40% TPAOH aqueous solution
NaAlO2, continues stirring and obtains mixed solution；Tetraethyl orthosilicate is added dropwise into mixed solution, stirring makes positive silicic acid tetrem
Crystallization 3 days, centrifuge washing, drying, roasting at 170 DEG C, are made ZSM-5 molecular sieve after ester hydrolysis is complete；
(2) ZSM-5 molecular sieve is mixed evenly with alkaline substance solution, then heats to 80-200 DEG C, continue to stir
5-200h is reacted, after the completion of reaction, centrifuge washing is dried, roasting, obtain bivalve layer ZSM-5 molecular sieve；
(3) bivalve obtained above layer ZSM-5 molecular sieve is fixed on to the stage casing of micro fixed-bed reactor, glycerine is passed through water-soluble
Before liquid, it is passed through at 270-300 DEG C after nitrogen purging catalyst 20-30min, glycerine water solution is injected into instead by syringe pump
Answer in device, with bivalve layer ZSM-5 molecular sieve haptoreaction after gasifying through helical groove, taken in after mixture of reaction products is condensed
In collector, timing sampling carries out qualitative and quantitative analysis through gas-chromatography.
2. the method that layer ZSM-5 molecular sieve dehydrating glycerin with catalyst in bivalve as claimed in claim 1 prepares methacrylaldehyde, its feature exists
In in step (1), the deionized water, the TPAOH aqueous solution, NaAlO2, the mass ratio of tetraethyl orthosilicate are：
(10.05-10.40)g：(9.12-9.17)g：(0.325-0.328)g：(20.80-20.85)g.
3. the method that layer ZSM-5 molecular sieve dehydrating glycerin with catalyst in bivalve as claimed in claim 1 prepares methacrylaldehyde, its feature exists
In：In step (2), the alkaline matter is the mixture of quaternary ammonium salt and sodium hydroxide, and the two mol ratio is 1:1.
4. the method that layer ZSM-5 molecular sieve dehydrating glycerin with catalyst in bivalve as claimed in claim 1 prepares methacrylaldehyde, its feature exists
In：In step (2), the alkaline matter is the mixture of quaternary ammonium salt and potassium hydroxide, and the two mol ratio is 1:1.
5. the method that layer ZSM-5 molecular sieve dehydrating glycerin with catalyst in bivalve as claimed in claim 1 prepares methacrylaldehyde, its feature exists
In：In step (2), the alkaline matter is the mixing of one or both of n-butylamine, quaternary ammonium base.
6. the method that the bivalve layer ZSM-5 molecular sieve dehydrating glycerin with catalyst as described in claim 3 or 4 prepares methacrylaldehyde, it is special
Levy and be：In step (2), the quaternary ammonium salt is 4 bromide, tetraethylammonium bromide, 4-propyl bromide and tetrabutyl bromine
Change the one or more in ammonium.
7. the method that layer ZSM-5 molecular sieve dehydrating glycerin with catalyst in bivalve as claimed in claim 5 prepares methacrylaldehyde, its feature exists
In：The quaternary ammonium base is the one or more in TMAH, tetraethyl ammonium hydroxide and TBAH.
8. the method that layer ZSM-5 molecular sieve dehydrating glycerin with catalyst in bivalve as claimed in claim 1 prepares methacrylaldehyde, its feature exists
In：In step (2), the sintering temperature is 500-900 DEG C, and roasting time is 1-12h.
9. the method that layer ZSM-5 molecular sieve dehydrating glycerin with catalyst in bivalve as claimed in claim 1 prepares methacrylaldehyde, its feature exists
In：In step (3), the concentration of the glycerine water solution is 10-20%.
10. the method that layer ZSM-5 molecular sieve dehydrating glycerin with catalyst in bivalve as claimed in claim 1 prepares methacrylaldehyde, its feature
It is：In step (3), the speed that the glycerine water solution is injected into reactor is 5-15ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710240117.0A CN106966878A (en) | 2017-04-13 | 2017-04-13 | The method that the bivalve layer molecular sieve catalytic dehydrating glycerins of ZSM 5 prepare methacrylaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710240117.0A CN106966878A (en) | 2017-04-13 | 2017-04-13 | The method that the bivalve layer molecular sieve catalytic dehydrating glycerins of ZSM 5 prepare methacrylaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106966878A true CN106966878A (en) | 2017-07-21 |
Family
ID=59333909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710240117.0A Withdrawn CN106966878A (en) | 2017-04-13 | 2017-04-13 | The method that the bivalve layer molecular sieve catalytic dehydrating glycerins of ZSM 5 prepare methacrylaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106966878A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947786A (en) * | 2018-07-10 | 2018-12-07 | 中国科学院青岛生物能源与过程研究所 | A kind of method of preparing acrolein by dehydrating glycerin |
| CN109836320A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of method that dehydrating glycerin prepares methacrylaldehyde |
| CN113856744A (en) * | 2021-11-04 | 2021-12-31 | 中国环境科学研究院 | Atom-doped modified double-shell monolithic hollow catalyst, and preparation method and application thereof |
| CN113856748A (en) * | 2021-11-04 | 2021-12-31 | 中国环境科学研究院 | Hollow ZSM-5 catalyst with atom-doped and metal cluster double-modified inner surface, and preparation method and application thereof |
| CN115286495A (en) * | 2022-08-23 | 2022-11-04 | 江西师范大学 | Method for preparing acrolein by catalytic oxidation of glycerol through ZSM-5 molecular sieve membrane |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417928A (en) * | 2008-12-09 | 2009-04-29 | 江苏工业学院 | Method for preparing acrylic aldehyde by biological glycerol dehydration |
| CN103100406A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst |
| CN103521256A (en) * | 2013-10-07 | 2014-01-22 | 上海华谊丙烯酸有限公司 | Molecular sieve catalyst for catalyzing and dehydrating glycerin to prepare acraldehyde and preparation method of molecular sieve catalyst |
| CN103638965A (en) * | 2013-12-27 | 2014-03-19 | 复旦大学 | Hierarchical porous ZSM-5 zeolite catalyst for preparing acrolein through glycerin dehydration as well as preparation method and application of hierarchical porous ZSM-5 zeolite catalyst |
| CN104841473A (en) * | 2015-04-21 | 2015-08-19 | 东南大学 | Preparation method of alcohol aromatization catalyst |
| CN105621452A (en) * | 2016-03-05 | 2016-06-01 | 复旦大学 | Multistage pore ZSM-5 catalyst for preparing acrolein by glycerol dehydration and preparation method of catalyst |
| CN106082257A (en) * | 2016-06-08 | 2016-11-09 | 清华大学 | A kind of hollow molecular sieve, preparation method and applications |
-
2017
- 2017-04-13 CN CN201710240117.0A patent/CN106966878A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417928A (en) * | 2008-12-09 | 2009-04-29 | 江苏工业学院 | Method for preparing acrylic aldehyde by biological glycerol dehydration |
| CN103100406A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst |
| CN103521256A (en) * | 2013-10-07 | 2014-01-22 | 上海华谊丙烯酸有限公司 | Molecular sieve catalyst for catalyzing and dehydrating glycerin to prepare acraldehyde and preparation method of molecular sieve catalyst |
| CN103638965A (en) * | 2013-12-27 | 2014-03-19 | 复旦大学 | Hierarchical porous ZSM-5 zeolite catalyst for preparing acrolein through glycerin dehydration as well as preparation method and application of hierarchical porous ZSM-5 zeolite catalyst |
| CN104841473A (en) * | 2015-04-21 | 2015-08-19 | 东南大学 | Preparation method of alcohol aromatization catalyst |
| CN105621452A (en) * | 2016-03-05 | 2016-06-01 | 复旦大学 | Multistage pore ZSM-5 catalyst for preparing acrolein by glycerol dehydration and preparation method of catalyst |
| CN106082257A (en) * | 2016-06-08 | 2016-11-09 | 清华大学 | A kind of hollow molecular sieve, preparation method and applications |
Non-Patent Citations (1)
| Title |
|---|
| 张卿，张兰兰，胡思，雍晓静，阿古达木，巩雁军，窦涛: "不同铝源合成ZSM-5分子筛及其MTP催化性能", 《石油学报（石油加工）》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836320A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of method that dehydrating glycerin prepares methacrylaldehyde |
| CN109836320B (en) * | 2017-11-29 | 2022-03-18 | 中国科学院大连化学物理研究所 | Method for preparing acrolein by glycerol dehydration |
| CN108947786A (en) * | 2018-07-10 | 2018-12-07 | 中国科学院青岛生物能源与过程研究所 | A kind of method of preparing acrolein by dehydrating glycerin |
| CN108947786B (en) * | 2018-07-10 | 2021-10-08 | 中国科学院青岛生物能源与过程研究所 | Method for preparing acrolein by glycerol dehydration |
| CN113856744A (en) * | 2021-11-04 | 2021-12-31 | 中国环境科学研究院 | Atom-doped modified double-shell monolithic hollow catalyst, and preparation method and application thereof |
| CN113856748A (en) * | 2021-11-04 | 2021-12-31 | 中国环境科学研究院 | Hollow ZSM-5 catalyst with atom-doped and metal cluster double-modified inner surface, and preparation method and application thereof |
| CN113856748B (en) * | 2021-11-04 | 2022-12-16 | 中国环境科学研究院 | Hollow ZSM-5 catalyst with atom-doped and metal cluster double-modified inner surface, and preparation method and application thereof |
| CN115286495A (en) * | 2022-08-23 | 2022-11-04 | 江西师范大学 | Method for preparing acrolein by catalytic oxidation of glycerol through ZSM-5 molecular sieve membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106966878A (en) | The method that the bivalve layer molecular sieve catalytic dehydrating glycerins of ZSM 5 prepare methacrylaldehyde | |
| CN101348430B (en) | Method for preparing acetylpropionic acid by solid superacid catalysis of stalk | |
| CN100548472C (en) | Core-shell type TiO 2The preparation method of/ZnO photochemical catalyst | |
| CN101475544A (en) | Method for preparing furan chemical by catalytic pyrolysis of biomass | |
| CN1935946A (en) | Method for preparing biodiesel by microwave assisted lewis base catalysis | |
| CN102744053A (en) | Composite solid base CaO-Al2O3 and method for preparing biodiesel oil by catalysis of waste vegetable oil with the same | |
| CN105197886A (en) | Method for catalyzing formic acid for dehydrogenation by use of supported Au-Pd/mpg-C3N4 nano-catalyst | |
| CN101428211B (en) | Catalyst for producing dimethoxymethane with methanol selective oxidation and preparation method thereof | |
| CN105289655A (en) | Solid acid catalyst HSO3-C/Fe3O4-graphene-Fe3O4/C-SO3H preparation method and method thereof for catalyzing hydrolysis of cellulose | |
| CN102702166A (en) | Method for preparing glycerin shrinkage benzaldehyde | |
| CN101798264A (en) | Method for preparing ethyl acetate by using alumina supported phosphotungstic acid as catalyst | |
| CN101786943A (en) | Catalytic synthesis method for preparing cresol by toluene one-step hydroxylation reaction | |
| CN103073526B (en) | Preparation method of 2, 5-disubstituted tetrahydrofuran mixture | |
| CN103657653B (en) | A kind of solid acid catalyst C/Fe3O4The method of MWCNTs and catalyzing cellulose hydrolysis thereof | |
| CN1974001A (en) | Polyoxometallate catalyst for preparing biological diesel oil | |
| CN105080606A (en) | Polyoxometallate catalyst for preparing biodiesel | |
| CN102093173A (en) | Method for preparing 3-ethyoxyl-1,2-propylene glycol by directly esterifying glycerol and ethanol | |
| CN102153444B (en) | Method for preparing 1,3-diols | |
| CN107365250B (en) | A kind of method that levulic acid is converted into using lignocellulose biomass by hydrolyzation | |
| CN108212207B (en) | Solid acid catalyst for preparing methyl lactate by catalytic conversion of glucose and preparation method thereof | |
| CN104164304B (en) | A kind of modified resin catalysis prepares the new method of biodiesel | |
| CN112354563B (en) | Carbon catalyst loaded with phosphotungstic acid, and preparation method and application thereof | |
| CN108467374A (en) | The method that furfural hydrogenation reaction prepares biological furans is carried out in fixed bed reactors | |
| CN115181002B (en) | Method for preparing alkane by biomass-based furfural in one step | |
| CN105312065A (en) | Preparation method of solid acid catalyst HSO3-C/graphene/C-SO3H and method of the catalyst in catalysis of cellulose hydrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20170721 |
|
| WW01 | Invention patent application withdrawn after publication |