CN110354899A - A kind of solid acid catalyst and preparation method and the application in epoxide hydration - Google Patents
A kind of solid acid catalyst and preparation method and the application in epoxide hydration Download PDFInfo
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- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The present invention relates to a kind of solid acid catalyst and preparation method and in the application of epoxide hydration, the solid acid catalyst is using ionic liquid, sodium p styrene sulfonate and crosslinking agent as raw material, it is obtained through free radical polymerization and sulfuric acid acidification reaction, single acid and good stability with moderate strength, can be swollen in water and be self-assembly of three-dimensional class honeycomb-like network structure.In the application that catalytic epoxy compound hydration prepares glycol, solid acid catalyst of the present invention shows excellent catalytic performance, its catalytic activity is worked as with inorganic acid catalyst sulfuric acid phase, and is significantly higher than traditional solid acid catalyst, such as: ion exchange resin Amberlite IR-120.Solid acid catalyst of the present invention can solve the problems such as inorganic acid catalyst bring equipment burn into energy consumption is high, environmental pollution is serious, and conventional solid acid catalyst stability is poor, the low defect of activity, so as to be prepared in the industrial production of glycol for epoxide hydration.
Description
Technical field
The invention belongs to heterogeneous catalysis technology fields, and in particular to a kind of solid acid catalyst and preparation method and in epoxy
Application in hydrate.
Background technique
Ethylene glycol is a kind of highly important Elementary Chemical Industry raw material, mainly for the production of polyester resin, polyester dacron, synthesis
Fiber, surfactant, antifreeze and thawing solution etc..Its industrial production is related to the numerous areas of national economy, affects
The development of petrochemical industry and the safety of the energy have great war to support infrastructural industry for the national economy and strategic new industry
Slightly meaning.Currently, the industrial production of ethylene glycol mainly has epoxyethane method, bioanalysis and synthesis gas method.Wherein, pass through epoxy second
The ethylene glycol of alkane method production accounts for about the 90% of ethylene glycol total output, and the ethylene glycol of polyester grade is still all produced by this method
(chemical industry progress, 2014,33 (07), 1740-1747).
There are mainly two types of the process routes that ethylene glycol is prepared using ethylene oxide as raw material: it is legal that one is epoxyethane waters,
I.e. ethylene oxide reacts under certain conditions with water generates ethylene glycol, can be subdivided into two kinds of works of direct hydration and catalysis hydration
Skill；Another kind is that ethylene carbonate ester process, i.e. ethylene oxide and carbon dioxide reaction generate ethylene carbonate, and ethylene carbonate passes through again
Hydrolysis or alcoholysis produce ethylene glycol.
Currently, ethylene oxide direct hydration method is the main method of industrial production ethylene glycol.But this method there is
Problems, such as: process flow is long, energy consumption is high, molar ratio (20~25:1) height, the economic effect of reaction feed water and ethylene oxide
Benefit is poor.Although vast researcher continuously improves production technology, drawbacks described above all can not be thoroughly overcome.In order to
Energy consumption can be fundamentally reduced, the selectivity of ethylene glycol is improved, researcher turns to ethylene oxide catalytic hydration one after another
With the research of ethylene carbonate ester process.
There is catalyzing epoxyethane hydration method good prospects for commercial application to have numerous catalyst systems so far and be reported
Road can be divided mainly into two major classes: (1) homogeneous catalyst: inorganic acid (such as: sulfuric acid), alkali metal, alkaline earth metal halide salt/carbonic acid
Salt/bicarbonate/sulfate etc.；(2) heterogeneous catalyst: ion exchange resin (such as: Amberlite IR-120), metal oxidation
Object is (such as: Nb2O5/Al2O3), molecular sieve (such as: H-ZSM-5), heteropoly acid is (such as: H3PW12O40) etc. (Chemical Society
Reviews,2012,41,4218-4244).But there is many defects for these catalyst systems, wherein 1. inorganic acid is (such as: sulphur
Acid) use can corrode equipment, pollution environment, and while post-processing, needs to be added a large amount of alkali and carrys out neutralization reaction liquid, this increases
The difficulty and production cost of separating technology are added；2. homogeneous catalyst, due to that can dissolve in the reaction system, this, which will lead to, urges
The quality problems of the loss of agent and separation problem and product；3. the thermal stability of ion exchange resin is poor, service life
It is short；4. reaction temperature needed for oxide carried type catalyst and pressure are all higher；5. molecular sieve poor selectivity, easy in inactivation；⑥
The use of heteropolyacid catalyst generally requires high water and molar ratio, this brings big energy to the separation of ethylene glycol
Consumption.Drawbacks described above makes these catalyst systems be difficult to apply in the industrial production of ethylene glycol.Therefore, novel height is developed
It imitates, the solid acid catalyst of high stability is the key that preparing ethandiol by catalyzing epoxyethane hydration.
Summary of the invention
The object of the present invention is to provide a kind of solid acid catalyst and preparation methods and answering in epoxide hydration
With.The solid acid catalyst is using ionic liquid, sodium p styrene sulfonate and crosslinking agent as raw material, through free radical polymerization and sulfuric acid acid
Change reaction to obtain, the single acid and good stability with moderate strength can be swollen and be self-assembly of in water
Three-dimensional class honeycomb-like network structure.Based on these features, which prepares the anti-of glycol in epoxide hydration
Excellent catalytic performance is shown in answering, catalytic activity is worked as with liquid acid catalyst sulfuric acid phase, and is significantly higher than traditional consolidate
Body acid catalyst, such as: molecular sieve H-ZSM-5 and ion exchange resin Amberlite IR-120.And the solid acid catalyst
It is easily recycled, the conversion ratio after being recycled for multiple times in hydration reaction and selectivity have no significant change.
Realizing the specific technical solution of the object of the invention is:
A kind of preparation method of solid acid catalyst, feature is: ionic liquid, sodium p styrene sulfonate and crosslinking agent is molten
Solution is warming up to 80 DEG C in deionized water, and initiator is added, obtains the precursor of solid acid catalyst through free radical polymerization, will before
Body is placed in the aqueous sulfuric acid that concentration is 1.0 mol/Ls, is stirred to react at room temperature 24 hours, after reaction, washing is dry
It is dry to get arrive the solid acid catalyst；Wherein:
Ionic liquid of the present invention is 1- vinyl -3- (3 '-sulfonic group) propyl imidazole salt, chemical structure such as formula
(I) shown in, 1- (3 '-sulfonic group) propyl -4-vinylpridine salt, shown in chemical structure such as formula (II) or (3 '-sulfonic acid
Base) propyl triallyl ammonium, shown in chemical structure such as formula (III)；
Crosslinking agent of the present invention is 1,8- triethylene glycol base -3, and 3 '-bi-vinyl imidazoles bromides, chemical structure is such as
Shown in formula (IV), N, N '-methylene-bisacrylamide or ethylene glycol diacrylate；
The molar ratio of ionic liquid of the present invention, sodium p styrene sulfonate and crosslinking agent is 1:0.5~2:0.05~1.
The quality of deionized water of the present invention is the ionic liquid, sodium p styrene sulfonate and crosslinking agent gross mass
2~5 times.
Initiator of the present invention is azodiisobutyronitrile or benzoyl peroxide.
The quality of initiator of the present invention is the 1 of the ionic liquid, sodium p styrene sulfonate and crosslinking agent gross mass
~10%.
The reaction time of free radical polymerization of the present invention is 12~48 hours.
Solid acid catalyst prepares the application in glycol in catalytic epoxy compound hydration, and feature is: by epoxide,
Deionized water and solid acid catalyst are placed in autoclave, closed, the air in discharge reaction kettle, and inflated with nitrogen to 0.01~
2.0 megapascal pressure are warming up to 80~120 DEG C, are stirred to react 0.25~2 hour, and after reaction, ice-water bath is cooling, passes through gas
Phase chromatography carries out quantitative analysis to reaction solution；Wherein:
Epoxide of the present invention is ethylene oxide, propylene oxide, epoxychloropropane or styrene oxide.
The molar ratio of epoxide of the present invention and the deionized water is 1:1~20.
The mole dosage of solid acid catalyst of the present invention be the epoxide mole dosage 0.01~
0.2%.
The invention has the following advantages that (1) described solid acid catalyst can be swollen in reaction substrate water and self assembly
Three-dimensional class honeycomb-like network structure is formed, can not only acid site farthest be exposed, additionally it is possible to accelerate reaction substrate
Contact with acid site, so that catalytic activity be greatly improved；(2) solid acid catalyst has single acid site, this makes
Obtain it has preferable selectivity in the hydration reaction of epoxide；Such as: the selectivity of the solid acid catalyst is far high
In the molecular sieve catalyst H-ZSM-5 with polyacid center；(3) the solid acid catalyst preparation is simple, stability is good, is easy to
It recycles, rear catalytic performance is recycled for multiple times without substantially changeing；(4) solid acid catalyst is stale-proof to production equipment
Erosion, no pollution to the environment；(5) solid acid catalyst is suitable for the catalysis hydration of a variety of epoxides, including epoxy second
Alkane, propylene oxide, epoxychloropropane and styrene oxide etc..
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of solid acid catalyst A prepared by the embodiment of the present invention 1；
Fig. 2 is the electron cryo-microscopy of external morphology after solid acid catalyst A prepared by the embodiment of the present invention 1 is swollen in water
Figure；
Fig. 3 is solid acid catalyst A's prepared by the embodiment of the present invention 1 and ion exchange resin Amberlite IR-120
Thermogravimetric analysis figure；
Fig. 4 is solid acid catalyst A prepared by the embodiment of the present invention 1 and molecular sieve H-ZSM-5 and probe molecule trimethyl
Solid state nmr phosphorus spectrogram after phosphine oxide interaction；(note: asterisk indicates spinning side band in figure, and chemical shift is 43 and 33ppm's
Signal peak is belonging respectively to the trimethylphosphine oxide (TMPO) of crystalline state trimethylphosphine oxide (TMPO) and physical absorption, and ownership is according to document
ChemicalReviews,2017,117,12475-12531)。
Specific embodiment
In conjunction with following specific embodiments, the present invention is described in further detail, and of the invention protects content not limit to
In following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that variation and excellent
Point is all included in the present invention, and using appended claims as protection scope.Implement process of the invention, condition,
Reagent, experimental method etc. are among the general principles and common general knowledge in the art, this hair in addition to what is specifically mentioned below
It is bright that there are no special restrictions to content.
Embodiment 1: the preparation of solid acid catalyst A
By 1.05 grams of 1- vinyl -3- (3 '-sulfonic group) propyl imidazole salt, 1.00 grams of sodium p styrene sulfonates, 0.12
Gram 1,8- triethylene glycol base -3,3 '-bi-vinyl imidazoles bromides are dissolved in 5 milliliters of deionized water, are warming up to 80 DEG C, add
Enter 0.11 gram of azodiisobutyronitrile, at 80 DEG C, is stirred to react 24 hours.The precursor of solid acid catalyst is obtained after reaction,
It is repeatedly washed with deionized water, methanol and acetone, it is dry.It is 1.0 mol/Ls that precursor after drying, which is placed in 100 milliliters of concentration,
Aqueous sulfuric acid in, be stirred to react 24 hours, after reaction, repeatedly washed with deionized water at room temperature, until cleaning solution
It is in neutrality, is subsequently dried, solid acid catalyst can be obtained, and be named as A, yield 84%.It is tested through swellbility, A exists
Swellbility in water is 24.5 gram grams.The pattern of A is characterized by scanning electron microscope；Refering to fig. 1, the A under drying regime is a kind of nothing
The micron order block of pore structure.Internal structure under A solvent swelling state is characterized by electron cryo-microscopy；Referring to Fig.2, under solvent swelling state
A has unique three-dimensional class honeycomb-like network structure.It is bright by the scanning electron microscope (SEM) photograph and electron cryo-microscopy chart of A, when A is molten in water
When swollen, A is self-assembled into three-dimensional class honeycomb-like network structure from non-porous structure.The stability of A is characterized by thermogravimetric analysis；Refering to
The temperature of initial decomposition of Fig. 3, A are 300 DEG C, much higher than commercial ion exchange resin Amberlite IR-120 (245 DEG C).A
Acid strength pass through solid state nmr phosphorus stave levy；Refering to Fig. 4, single acid site of the A with moderate strength, and commercial molecular sieve
H-ZSM-5 possesses the different a variety of acid sites of intensity.
Embodiment 2: the preparation of solid acid catalyst B
The present embodiment intermediate ion liquid is 1- (3 '-sulfonic group) propyl -4-vinylpridine salt (1.02 grams), to benzene second
Alkene sodium sulfonate (0.93 gram), 1,8- triethylene glycol base -3,3 '-bi-vinyl imidazoles bromide (0.46 gram), azodiisobutyronitrile
Solid acid catalyst B, yield 79% is prepared with embodiment 1 in (0.12 gram), other preparation conditions and method.Through being swollen
Degree test, the swellbility of B in water are 29.1 gram grams.
Embodiment 3: solid acid catalyst A catalytic epoxyethane water conjunction prepares ethylene glycol
A (0.031 gram), ethylene oxide (2.20 grams, 50 mMs) and water (9.01 grams, 500 mMs) are placed in and are equipped with
It is closed in 50 milliliters of autoclaves of magneton, the air in reaction kettle is discharged, inflated with nitrogen is warming up to 1.0 megapascal pressure
It 100 DEG C, is then stirred to react at 100 DEG C 0.5 hour.After reaction, ice-water bath is cooling, by gas-chromatography to reaction solution
Quantitative analysis is carried out, determines that the conversion ratio of ethylene oxide is 95%, the selectivity of target product ethylene glycol is 86%.Ethylene glycol
Structure is determining through NMR spectrum,1H NMR(400MHz,D2O, TMS) δ (ppm): 2.01 (t, J=6.0Hz, 4H)；13C
NMR(100MHz,D2O,TMS)δ(ppm):62.20。
Embodiment 4: comparative example
By catalyst (sour total amount is identical), ethylene oxide (2.20 grams, 50 mMs) and water (9.01 grams, 500 mMs)
It is placed in 50 milliliters of autoclaves equipped with magneton, closed, the air in discharge reaction kettle, inflated with nitrogen to 1.0 megapascal pressure,
100 DEG C are warming up to, is then stirred to react at 100 DEG C 0.5 hour.After reaction, ice-water bath is cooling, passes through gas-chromatography pair
Reaction solution carries out quantitative analysis, the results are shown in Table 1.
1 different catalysts catalytic epoxyethane water conjunction of table prepares ethylene glycol
Table 1 the result shows that, under identical reaction conditions, the catalytic activity of solid acid catalyst A and B are significantly higher than commercialization
Ion exchange resin Amberlite IR-120 and molecular sieve H-ZSM-5, and with homogeneous catalyst sulfuric acid and p-methyl benzenesulfonic acid
It is suitable.In addition, the single acid site of solid acid catalyst A and B make the selectivity of ethylene glycol much higher than the H- at polyacid center
ZSM-5。
Embodiment 5: the cycling and reutilization situation of solid acid catalyst A
Solid acid catalyst A is after catalytic epoxyethane water conjunction prepares glycol reaction, through acetone deswelling, centrifugation
Separation, acetone washing and vacuum drying, can be realized recycling.Reaction solution is added in solid acid catalyst A after the recovery, is carried out again
Primary catalysis.For other steps with described in embodiment 3, cycling and reutilization the results are shown in Table 2.
The cycling and reutilization situation of 2 solid acid catalyst A of table
| Cycle-index | 1 | 2 | 3 | 4 | 5 |
| Ethylene oxide conversion ratio/% | 95 | 95 | 94 | 93 | 95 |
| Glycol selectivity/% | 86 | 86 | 88 | 88 | 87 |
Table 2 the result shows that, solid acid catalyst A is after 5 circulations, and for catalytic activity without substantially changeing, this explanation should
Class solid acid catalyst has excellent cycling and reutilization performance.
Embodiment 6: solid acid catalyst A is catalyzed propylene oxide hydration preparation 1,2- propylene glycol
Epoxide is propylene oxide (2.90 grams, 50 mMs) in the present embodiment, and other reaction conditions and method are same
Embodiment 3.Quantitative analysis is carried out to reaction solution by gas-chromatography, determines that the conversion ratio of propylene oxide is 90%, 1,2- the third two
The selectivity of alcohol is 88%.The structure of 1,2-PD is determining through NMR spectrum,1H NMR(400MHz,CDCl3,TMS)δ
(ppm): 3.83-3.90 (m, 1H), 3.79 (s, 2H), 3.55-3.90 (m, 1H), 3.32-3.38 (m, 1H), 1.12 (d, J=
6.0Hz,3H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm):68.3,67.9,18.7。
Embodiment 7: solid acid catalyst A Epichlorohydrin hydration preparation 3- chlorine 1,2- propylene glycol
Epoxide is epoxychloropropane (4.63 grams, 50 mMs), other reaction conditions and method in the present embodiment
With embodiment 3.Quantitative analysis is carried out to reaction solution by gas-chromatography, determines that the conversion ratio of epoxychloropropane is that 89%, 3- is chloro-
The selectivity of 1,2- propylene glycol is 90%.The structure of 3- chlorine-1,2-propylene glycol is determining through NMR spectrum,1H NMR
(400MHz,CDCl3,TMS)δ(ppm):3.94(s,1H),3.77–3.80(m,1H),3.59–3.70(m,3H),2.63(s,
1H),2.05(s,1H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm):71.74,63.57,45.56。
Embodiment 8: solid acid catalyst A catalysis oxidation styrene hydration prepares phenyl -1,2- ethylene glycol
Epoxide is styrene oxide (6.01 grams, 50 mMs), other reaction conditions and method in the present embodiment
With embodiment 3.Quantitative analysis is carried out to reaction solution by gas-chromatography, determines that the conversion ratio of styrene oxide is 97%, phenyl-
The selectivity of 1,2- ethylene glycol is 95%.Phenyl -1,2-PD structure is determining through NMR spectrum,1H NMR
(400MHz,CDCl3, TMS) and δ (ppm): 7.31-7.37 (m, 5H), 4.83 (dd, J=3.2,8.0Hz, 1H), 3.76 (dd, J=
3.0,11.4Hz, 1H), 3.66 (dd, J=8.2,11.1Hz, 1H), 2.69 (s, 1H), 2.27 (s, 1H)；13C NMR(100MHz,
CDCl3,TMS)δ(ppm):140.34,128.36,127.77,126.00,74.63,67.88。
Claims (8)
1. a kind of preparation method of solid acid catalyst, which is characterized in that by ionic liquid, sodium p styrene sulfonate and crosslinking agent
It is dissolved in deionized water, is warming up to 80 DEG C, initiator is added, obtains the precursor of solid acid catalyst through free radical polymerization, it will
Precursor is placed in the aqueous sulfuric acid that concentration is 1.0 mol/Ls, is stirred to react at room temperature 24 hours, after reaction, washing is dry
It is dry to get arrive the solid acid catalyst；Wherein:
The molar ratio of the ionic liquid, sodium p styrene sulfonate and crosslinking agent is 1:0.5~2:0.05~1；
The quality of the deionized water is 2~5 times of the ionic liquid, sodium p styrene sulfonate and crosslinking agent gross mass；
The quality of the initiator is the 1~10% of the ionic liquid, sodium p styrene sulfonate and crosslinking agent gross mass；
The reaction time of the free radical polymerization is 12~48 hours.
2. the preparation method of solid acid catalyst according to claim 1, which is characterized in that the ionic liquid is 1-
Vinyl -3- (3 '-sulfonic group) propyl imidazole salt, shown in chemical structure such as formula (I), 1- (3 '-sulfonic group) propyl -4- second
Alkenyl pyridiniujm, shown in chemical structure such as formula (II) or (3 '-sulfonic group) propyl triallyl ammonium, chemical structure is such as
Shown in formula (III)；
3. the preparation method of solid acid catalyst according to claim 1, which is characterized in that the crosslinking agent is 1,8- tri-
3,3 '-bi-vinyl imidazoles bromide of ethylene glycol-, shown in chemical structure such as formula (IV), N, N '-methylene-bisacrylamide
Or ethylene glycol diacrylate；
4. the preparation method of solid acid catalyst according to claim 1, which is characterized in that the initiator is azo two
Isobutyronitrile or benzoyl peroxide.
5. solid acid catalyst made from a kind of claim 1 the method.
6. solid acid catalyst described in a kind of claim 5 prepares the application in glycol in catalytic epoxy compound hydration.
7. application according to claim 6, which is characterized in that by epoxide, deionized water and solid acid catalyst
It is placed in autoclave, it is closed, it is discharged the air in reaction kettle, inflated with nitrogen to 0.01~2.0 megapascal pressure, it is warming up to 80~
It 120 DEG C, is stirred to react 0.25~2 hour, after reaction, ice-water bath is cooling, is quantified by gas-chromatography to reaction solution
Analysis；Wherein:
The molar ratio of the epoxide and the deionized water is 1:1~20；
The mole dosage of the solid acid catalyst is the 0.01~0.2% of the epoxide mole dosage.
8. application according to claim 6, which is characterized in that the epoxide is ethylene oxide, propylene oxide, ring
Oxygen chloropropane or styrene oxide.
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| CN113019446A (en) * | 2020-06-29 | 2021-06-25 | 中国科学院过程工程研究所 | Preparation method and application of mesoporous polar functionalized polyion liquid-heteropoly acid catalyst |
| CN116371464A (en) * | 2023-02-10 | 2023-07-04 | 华东师范大学 | Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application |
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