CN103922893B - A kind of composite catalyst hydrogenolysis catalysis of glycerin prepares the method for 1,2-PD - Google Patents
A kind of composite catalyst hydrogenolysis catalysis of glycerin prepares the method for 1,2-PD Download PDFInfo
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- CN103922893B CN103922893B CN201410158027.3A CN201410158027A CN103922893B CN 103922893 B CN103922893 B CN 103922893B CN 201410158027 A CN201410158027 A CN 201410158027A CN 103922893 B CN103922893 B CN 103922893B
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000007306 functionalization reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 22
- 239000010970 precious metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- -1 cupric Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- 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
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of under dual-function composite catalyst effect glycerine intermittent type hydrogenolysis prepare the method for 1,2-PD.It is characterized in that the dehydration-hydrogenation mechanism based on hydrogenolysis of glycerin, adopt acid function to mix multiclass ionic liquid [HMIM]
3pW
12o
40as catalytic dehydration center, commodity RaneyNi is shortening center, is coupled into dual-function composite catalyst and prepares 1,2-PD for the hydrogenolysis of glycerine.Assorted multiclass ionic liquid [HMIM]
3pW
12o
40have and be partially soluble in reaction system at reaction conditions, the probability of acid site and glycerol hydroxy groups contact activation is increased, and reaction is separated out after terminating and is recovered solid-state character from system, can together with RaneyNi from reactant simple separation.This catalytic hydrogenolysis has that catalyst preparing is simple, with low cost, without the need to high temperature reduction, advantages of environment protection, for glycerin catalytic hydrogenolysis provides an effective new way.
Description
Technical field
The present invention relates to a kind of method of hydrogenolysis catalysis of glycerin, adopt acid functionalization to mix multiclass ionic liquid [HMIM] specifically
3pW
12o
40the dual-function composite catalyst be coupled into commodity RaneyNi, in batch reactor, the method for 1,2-PD prepared by hydrogenolysis glycerine.
Background technology
Along with the fast development of biofuel in world wide, the application of a large amount of glycerin by-product becomes the key determining biofuel economy; Meanwhile, the demand of glycerine derived product propylene glycol is also rising steadily.1,2-PD and 1,3-PD are all widely used industrial chemicals and good solvent, antifreezing agent, and wherein 1,2-PD is the important source material of unsaturated polyester, epoxy resin, urethane; 1,3-PD is the key precursor preparing high-performance polyester PTT.The industrial process of propylene glycol product is raw material mainly with petroleum-based propylene oxide etc., and facility investment is large, and technical difficulty is high, and catalyst system is complicated.For propylene glycol product development to the requirement of synthesis new way and Biodiesel development need, hydrogenolysis of glycerin deep processing has become guarantee and the research and development focus of oil prodution industry and biofuel industry competition advantage.
Glycerine chemistry legal system is more for 1,2-PD report, wherein based on the research that the precious metals such as Ru, Rh, Pt, Pd are catalyzer.As: adopt loading type Ru/TiO prepared by pickling process
2catalyzer ([J]. catalysis journal, 2011,32 (9): 1545-1549), under 170 DEG C of mild reaction conditions with 3MPa, take LiOH as additive, glycerol conversion yield and 1,2-PD selectivity reach 89.6% and 86.8% respectively.Although these use precious metal to have higher low temperature hydrogenation activity as the method for catalyzer, because of expensive, to reducing the cost of Biodiesel chain and improving having little significance of glycerine added value.
Relative to expensive noble metal catalyst, Cu, Ni, the base metals such as Co are paid close attention to widely with its cheap price, wherein, Cu is catalyst based because of its unique C-O key hydrogenolysis performance, for hydrogenolysis of glycerin prepares 1, the research main flow of 2-propylene glycol: Low-pressurehydrogenolysisofglyceroltopropyleneglycol [J] .AppliedCatalysisA:General, 2005, 281 (1-2): 225-231 report and adopt Cu-Cr catalyzer, glycerine carries out hydrogenolysis in two steps, at 200 DEG C, 200psi pressure, under 80% aqueous glycerin solution condition, first glycerine generate hydroxyacetone by dehydration, then hydrogenation obtains propylene glycol, 1, the yield of 2-propylene glycol reaches 73%, but the chromium metal that this catalyzer uses can cause environmental pollution.US5616817 adopts coprecipitation method preparation to produce propylene glycol containing the polycomponent catalytic hydrogenolysis glycerine of cobalt, copper, manganese and molybdenum, adds mineral acid to improve the mechanical property of catalyzer in the process of Kaolinite Preparation of Catalyst.Under the condition of temperature of reaction 240 ~ 280 DEG C, hydrogen pressure 25 ~ 35MPa, the transformation efficiency of glycerine is close to 100%, and the selectivity of 1,2-PD can reach 95%, requires higher under this condition to reaction pressure.CN4302464A utilizes the polycomponent supported catalyst of the compositions such as cupric, chromium, barium, silicon and manganese, and hydrogenolysis catalysis of glycerin, almost only generates 1,2-PD, but the preparation of catalyzer is comparatively complicated.
On the whole, at present for hydrogenolysis of glycerin reaction precious metal and non-precious metal catalyst be usually prepared into oxide form, and often need add various auxiliary agent with improves reaction selectivity and stability, catalyzer preparation complexity, poor reproducibility; Oxide catalyst need in the reduction of reaction process situ to obtain hydrogenation activity, and need higher reduction temperature, energy consumption is high.Therefore developing a kind of preparation effective catalyst simple, with low cost that adopts and prepare propylene glycol for hydrogenolysis of glycerin, is the current demand of Biodiesel development and glycerine field of deep.
Summary of the invention
The present invention adopts acid functionalization to mix multiclass ionic liquid [HMIM]
3pW
12o
40as catalytic dehydration center, commodity RaneyNi, as shortening center, is coupled into dual-function composite catalyst, and in batch reactor, 1,2-PD prepared by hydrogenolysis glycerine.There is reactions steps in hydrogenolysis of glycerin process simple, the advantages such as convenient post-treatment.
The object of this invention is to provide a kind of cheap, preparation is simple, be applied to without the need to high temperature reduction, the gentle segregative dual-function composite catalyst of operational condition the method that hydrogenolysis of glycerin prepares 1,2-PD.
Technical scheme of the present invention is as follows:
The method of the composite catalyst preparing 1,2-propylene glycol by catalytic hydrogenolysis of glycerin described in technical solution of the present invention is carried out in batch autoclave reactor, and raw material is aqueous glycerin solution:
In 75mL stainless steel autoclave batch reactor, add 20g40% aqueous glycerin solution, and dual-function composite catalyst [HMIM]
3pW
12o
40(0.2mmol)/RaneyNi (0.3g), with nitrogen replacement air three times, then after using hydrogen exchange nitrogen three times, being filled with hydrogen to preliminary examination pressure is 6MPa, reacts 11h at being heated to 230 DEG C under magnetic agitation.After reaction terminates, the dual-function composite catalyst method of centrifugal decant is separated and direct reuse.
Dual-function composite catalyst [HMIM] described in technique scheme
3pW
12o
40/ RaneyNi, its preparation method is:
[HMIM]
3pW
12o
40/ RaneyNi catalyzer is that the mode by precipitating in aqueous is prepared [HMIM]
3pW
12o
40, then to be coupled with commodity RaneyNi in the mode simply mixed and to prepare.Wherein acid functionalization is mixed multiclass ionic liquid [HMIM]
3pW
12o
40preparation be adopt phospho-wolframic acid and N-Methylimidazole to be raw material, under stirring at room temperature condition, three times of amount of substance N-Methylimidazoles are added drop-wise in phosphotungstic acid aqueous solution, dropwise rear continuation room temperature reaction 24h, through suction filtration, washing, drying, obtain [HMIM]
3pW
12o
40white solid.By [HMIM]
3pW
12o
40with commodity RaneyNi according to 0.15gRaneyNi/mmol [HMIM]
3pW
12o
40ratio mix and obtain dual-function composite catalyst.
Composite catalyst described in technique scheme is before use without the need to activated pre-treatment.
Dual-function composite catalyst preparation method prepared by the present invention is simple, to mix multiclass ionic liquid [HMIM] with the acid function in reaction system with " high-temperature digestion, low temperature is separated out " performance
3pW
12o
40as catalytic dehydration center, active high, cost is low, be hydrogenation catalyst center without the need to the commodity RaneyNi of high temperature reduction, by the method preparation simply mixed.Overcome use precious metal and non-noble metal oxide class catalyzer cost higher, the shortcomings such as preparation is complicated, and working conditions is harsh.This catalyzer shows good catalytic activity and stability in hydrogenolysis of glycerin reaction, and reaction conditions is comparatively gentle, and technique is simple, and product is easy to be separated, and preparing 1,2-PD for glycerin catalytic hydrogenolysis provides a new effective way.
Specific implementation method
Just concrete embodiment further illustrates the inventive method below.
Embodiment 1
Catalyst preparing:
Phospho-wolframic acid 14.4g(0.005mol is added) in there-necked flask (100mL), moving into 15mL deionized water makes it dissolve completely, magnetic agitation drips 1.23g(0.015mol) N-Methylimidazole, room temperature reaction 24h after control dropwises in 30min, suction filtration, cleaning, drying, gained white solid is [HMIM]
3pW
12o
40.Before hydrogenolysis, by [HMIM]
3pW
12o
40with commodity RaneyNi according to 0.15gRaneyNi/mmol [HMIM]
3pW
12o
40ratio directly mix and add reactor, obtain dual-function composite catalyst.
Hydrogenolysis of glycerin reacts:
Adopt 75mL batch autoclave reactor, add 20g40% aqueous glycerin solution and 0.2mmol
[HMIM]
3pW
12o
40/ 0.3gRaneyNi composite catalyst, with nitrogen replacement air three times, then use hydrogen exchange nitrogen three times, being filled with hydrogen to preliminary examination pressure is 6MPa, reacts 11h at being heated to 230 DEG C under magnetic agitation.
After reaction terminates, adopt the mode of centrifugal decant by liquid form mixt and solid catalyst simple separation.Do gas chromatographic analysis after product mixtures sampling, the transformation efficiency of gained glycerine is 83.3%, and 1,2-PD selectivity is 57.3%; Catalyzer can directly be reused without the need to process, reuses rear glycerol conversion yield five times and 1,2-PD still can reach 76.9% and 50.7% respectively.
Claims (1)
1. composite catalyst hydrogenolysis catalysis of glycerin prepares a method for 1,2-PD, it is characterized in that: adopt acid functionalization to mix multiclass ionic liquid [HMIM]
3pW
12o
40as catalytic dehydration center, commodity RaneyNi is shortening center, is coupled into dual-function composite catalyst and prepares 1,2-PD for glycerine intermittent type hydrogenolysis;
Wherein said dual-function composite catalyst preparation method is: be added drop-wise in phosphotungstic acid aqueous solution by three times of amount of substance N-Methylimidazoles under stirring at room temperature condition, after dropwising rear continuation room temperature reaction 24h, suction filtration, washing, drying, obtain acid functionalization and to mix multiclass ionic liquid [HMIM]
3pW
12o
40white solid, according to every mmole [HMIM]
3pW
12o
40both mix by the ratio composite with 0.15g commodity RaneyNi, i.e. the dual-function composite catalyst of obtained hydrogenolysis of glycerin reaction, and this composite catalyst is before use without the need to activated pre-treatment;
Wherein said hydrogenolysis method is: adopt 75mL stainless steel autoclave batch reactor, add 40% aqueous glycerin solution of 20g, and by [HMIM] of 0.2mmol
3pW
12o
40with the dual-function composite catalyst that the RaneyNi of 0.3g is re-dubbed, with nitrogen replacement air three times, use hydrogen exchange nitrogen again three times, being filled with hydrogen to preliminary examination pressure is 6MPa, 11h is reacted at being heated to 230 DEG C, after reaction terminates, the dual-function composite catalyst method of centrifugal decant is separated and direct reuse.
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| CN201410158027.3A CN103922893B (en) | 2014-04-19 | 2014-04-19 | A kind of composite catalyst hydrogenolysis catalysis of glycerin prepares the method for 1,2-PD |
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| CN201410158027.3A CN103922893B (en) | 2014-04-19 | 2014-04-19 | A kind of composite catalyst hydrogenolysis catalysis of glycerin prepares the method for 1,2-PD |
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| CN103922893B true CN103922893B (en) | 2015-11-25 |
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| EP3197906B1 (en) * | 2014-09-26 | 2023-10-25 | Mebius d.o.o. | Processes for preparing polyoxometalate salts for use in proton exchange membranes and fuel cells |
| CN115551824A (en) * | 2020-05-18 | 2022-12-30 | 阿彻丹尼尔斯米德兰公司 | Process for the hydrogenolysis of glycerol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381280A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院大连化学物理研究所 | Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol |
| CN101407448A (en) * | 2008-11-07 | 2009-04-15 | 南京工业大学 | Method for continuously preparing 1, 3-propylene glycol by one-step conversion of glycerol |
| WO2013150305A2 (en) * | 2012-04-04 | 2013-10-10 | Isis Innovation Limited | Alcohol production process |
| JP2013216623A (en) * | 2012-04-10 | 2013-10-24 | Daicel Corp | Method for producing propanediol |
| CN103657730A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing 1,2-propylene glycol by glycerinum hydrogenation and preparation method thereof |
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