CN108212196B - A kind of preparation method and application of composite catalyst for synthesizing propylene glycol ether - Google Patents
A kind of preparation method and application of composite catalyst for synthesizing propylene glycol ether Download PDFInfo
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- CN108212196B CN108212196B CN201810040885.6A CN201810040885A CN108212196B CN 108212196 B CN108212196 B CN 108212196B CN 201810040885 A CN201810040885 A CN 201810040885A CN 108212196 B CN108212196 B CN 108212196B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000003277 amino group Chemical group 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 17
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 10
- 235000004279 alanine Nutrition 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 5
- -1 propylene glycol ether compound Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- ABFYEILPZWAIBN-UHFFFAOYSA-N 3-(iminomethylideneamino)-n,n-dimethylpropan-1-amine;hydrochloride Chemical compound Cl.CN(C)CCCN=C=N ABFYEILPZWAIBN-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910017906 NH3H2O Inorganic materials 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of chemical catalysis, and provides a preparation method of a composite catalyst for synthesizing propylene glycol ether, which comprises the following steps: preparing amino modified mesoporous nano silicon dioxide spheres; reacting the amino modified mesoporous nano silicon dioxide with succinic anhydride to obtain a carboxylated silicon carrier; and carrying out condensation reaction on the carboxylated silicon carrier and carbon points with amino groups on the surface to obtain the composite catalyst for catalytically synthesizing propylene glycol ether. The invention also provides the application of the composite catalyst for catalytically synthesizing the propylene glycol ether in preparing the propylene glycol ether by catalyzing alcohol and propylene oxide. The catalyst has the advantages of high activity, high selectivity, easy recovery, low energy consumption, reusability and the like.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a preparation method and application of a composite catalyst for synthesizing propylene glycol ether.
Background
The propylene glycol ether compound is a fine chemical with excellent performance and is also an environment-friendly high-grade solvent, two functional groups with strong solubility, namely hydroxyl and ether bond, are arranged in the structure of the propylene glycol ether compound, the former has hydrophilicity, and the latter has lipophilicity, so that the propylene glycol ether compound has strong dissolving capacity, is called as a universal solvent, and is widely applied to the industries of coatings, printing ink, paint, printing and the like. The propylene glycol ether compound is mainly synthesized by the reaction of propylene oxide and low-carbon alcohol, however, due to the steric effect of the propylene oxide, the ring-opening positions of the propylene glycol ether compound can be different under the conditions of acid and alkali, so that different alcohol ether products can be obtained, wherein the alkali generates 1-methoxy-2-propanol, and the acid generates 2-methoxy-1-propanol. Alcohol ether products catalyzed by bases are more environmentally friendly and are more and more concerned by people. At present, the synthesis routes of propylene glycol ether mainly comprise: williamson synthesis, acetal method, alkoxyepoxypropane method, epoxypropane method, and the like. The propylene oxide method, as a green and efficient synthesis method, has the advantages of high atom utilization rate, low operation risk and the like, and is the only synthesis route which is the most active in development and research and has already realized industrialization at present. The reaction system for synthesizing propylene glycol ether by propylene oxide method can be divided into homogeneous reaction system and heterogeneous reaction system. The homogeneous catalysis process is the method which is generally adopted in the industry at present, and the technology is relatively mature. The main homogeneous acidic catalysts are sulfuric acid, boron trifluoride and the like, while the basic catalysts are sodium hydroxide, sodium methoxide and the like. Homogeneous catalysts can achieve better yield and relatively narrow product distribution, but still face huge challenges due to problems of complex process, corrosion and the like. The heterogeneous catalysts are large at present and mainly comprise molecular sieves, montmorillonite, metal oxides and the like. Although the equipment is not corroded, the process flow is relatively simple, the reaction conditions are relatively harsh, and the product distribution is not uniform.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a preparation method and application of a composite catalyst for synthesizing propylene glycol ether.
The invention provides a preparation method of a composite catalyst for synthesizing propylene glycol ether, which comprises the following steps:
preparing amino modified mesoporous nano silicon dioxide spheres;
reacting the amino modified mesoporous nano silicon dioxide with succinic anhydride to obtain a carboxylated silicon carrier;
and carrying out condensation reaction on the carboxylated silicon carrier and carbon points with amino groups on the surface to obtain the composite catalyst for catalytically synthesizing propylene glycol ether.
The invention also provides the application of the composite catalyst for catalytically synthesizing the propylene glycol ether in preparing the propylene glycol ether by catalyzing alcohol and propylene oxide.
The composite catalyst obtained by the preparation method of the nano carbon dots for catalytically synthesizing propylene glycol ether provided by the invention has the advantages of high activity, high selectivity, easiness in recovery, low energy consumption, easiness in separation and the like. Compared with the existing solid catalyst, the catalyst has high efficiency and few byproducts. In addition, the catalyst has simple preparation process and low production cost, and is suitable for industrial production.
Drawings
FIG. 1 is a transmission electron microscope photograph of a composite catalyst for the catalytic synthesis of propylene glycol ether obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a composite catalyst for catalytically synthesizing propylene glycol ether, which comprises the following steps:
preparing amino modified mesoporous nano silicon dioxide spheres;
reacting the amino modified mesoporous nano silicon dioxide with succinic anhydride to obtain a carboxylated silicon carrier;
and carrying out condensation reaction on the carboxylated silicon carrier and carbon points with amino groups on the surface to obtain the composite catalyst for catalytically synthesizing propylene glycol ether.
Specifically, the amino-modified mesoporous nano-silica spheres can be obtained by the existing method, such as aminated MCM-41 and the like, and preferably, the diameter of the amino-modified mesoporous nano-silica spheres is 200-400 nm, the mesoporous size is distributed in the range of 4-10 nm, and if the size is too small, the carbon dot loading rate is reduced, the products are accumulated, and the catalytic effect is poor. The size of the carbon dots with amino groups on the surface is less than 5nm, and the small size of the carbon dots can improve the surface alkalinity and improve the catalytic effect.
More specifically, the preparation method of the amino modified mesoporous nano-silica spheres comprises the following steps:
adding hexadecyl trimethyl ammonium bromide into water, sequentially adding ammonia water, diethyl ether and ethanol after dissolving, uniformly stirring, adding tetraethoxysilane and 3-aminopropyl triethoxysilane, reacting for 4 hours at 20-25 ℃, centrifuging, washing and drying to obtain the amino modified mesoporous nano-silica spheres.
Preferably, the amino-modified mesoporous nano-silica reacts with succinic anhydride, specifically, the amino-modified mesoporous nano-silica is added into dimethyl sulfoxide, succinic anhydride and triethylamine are added, and stirring is carried out at 40 ℃ for 24-48 hours, so as to obtain the carboxylated silicon carrier.
Specifically, the preparation steps of the carbon dots with the amino groups on the surface are as follows:
dissolving alanine, ethylenediamine and/or polyethyleneimine in water to obtain a mixed solution, wherein the mass ratio of the alanine to the ethylenediamine and/or polyethyleneimine is (1-4): 1;
and placing the mixed solution in a closed reaction container, heating to 180-240 ℃, keeping for 6-24 hours, cooling, and drying a product to obtain the carbon dots with the amino groups on the surface.
Preferably, the mass ratio of the alanine to the ethylenediamine and/or the polyethyleneimine is 2-3: 1. specifically, the mixed solution is placed in a closed reaction container, and is preferably heated to 200 to 220 ℃. After cooling, the organic impurities are preferably removed by dialysis and then dried. More preferably, the carbon dots are made from alanine and ethylenediamine.
Dispersing the carboxylated silicon carrier and carbon points with amino groups on the surface in water, adding a (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and an N-hydroxysuccinimide (NHS) coupling agent, reacting for 2-12 h, or dispersing the carboxylated silicon carrier and the carbon points with amino groups on the surface in an organic solvent, adding Dicyclohexylcarbodiimide (DCC), and obtaining the composite catalyst for catalytically synthesizing propylene glycol ether.
The invention also provides the application of the composite catalyst for synthesizing the propylene glycol ether in preparing the propylene glycol ether by catalyzing alcohol and propylene oxide.
Specifically, propylene oxide and alcohol are fed into a reactor to contact with the composite catalyst, and are heated to 80-160 ℃ in a closed environment to obtain the propylene glycol ether. Wherein the mass ratio of the composite catalyst to the propylene oxide is 1: 10 to 1000.
Preferably, the heating mode is microwave heating, and the molar ratio of the propylene oxide to the alcohol is 1: 1-10, wherein the mass ratio of the composite catalyst to the propylene oxide is 1: 10-500, and the reaction time is 30-300 min. The pressure is usually between 0.1 and 1 MPa. More preferably, the molar ratio of the propylene oxide to the alcohol is 1: 3-5, and the mass ratio of the catalyst to the propylene oxide is 1: 20 to 100. Compared with the existing catalyst, the propylene glycol ether yield can be higher by adding 0.025-0.5 percent of the propylene oxide by mass. The alcohol is C1～C8Any one of alcohols. Compared with the existing solid catalyst, the composite catalyst has the advantages of greatly improved conversion rate of propylene oxide and selectivity of propylene glycol ether, reusability and low cost.
The preparation method and application of the composite catalyst for synthesizing propylene glycol ether are illustrated by the following specific examples. The raw materials in the following examples can be directly prepared according to the existing methods, and of course, the raw materials in other examples can also be directly purchased from the market, and are not limited thereto.
Example 1:
adding 2.5g of hexadecyl trimethyl ammonium bromide into 350mL of water, sequentially adding 4mL of ammonia water (30%), 75mL of diethyl ether and 25mL of ethanol after dissolving, stirring uniformly, adding 12.5mL of ethyl orthosilicate and 0.5mL of 3-aminopropyl triethoxysilane, reacting for 4 hours at 20-25 ℃, adding 1mL of concentrated hydrochloric acid to stop the reaction, immediately centrifuging and washing, and drying to obtain the amino modified mesoporous nano silicon dioxide ball.
2.67g of alanine was dissolved in 30mL of ultrapure water, and then 0.8mL of ethylenediamine was added while stirring, and then the above solution was transferred to a 50mL high-temperature reaction tank and heated to 200 ℃. After 6 hours of reaction, the reaction mixture was cooled at room temperature, and the product was placed in a dialysis bag (1000MWCO), dialyzed for 48 hours, and freeze-dried to obtain the carbon dots having amino groups on the surface.
And adding 90mg of amino modified mesoporous nano-silica spheres into 10mL of DMSO solution containing 40mg of succinic anhydride and 40mg of triethylamine, stirring for 48 hours at 40 ℃, centrifuging, and washing with ethanol to obtain the carboxylated silicon carrier.
80mg of the carboxylated silicon carrier was added to 6mL of an aqueous solution containing 50mg of EDC and 20mg of NHS, and then 6mg of carbon dots containing amino groups on the surface were added at room temperature and stirred for 8 hours for centrifugation to obtain the composite catalyst for synthesizing propylene glycol ether, which is shown in FIG. 1 in a transmission electron microscope.
Adding the composite catalyst of the epoxy propane, the methanol and the synthetic propylene glycol ether into a microwave reaction tube, wherein the molar ratio of the epoxy propane to the methanol is 1: 7, the mass ratio of the composite catalyst to the propylene oxide is 1: 30. heating to 120 ℃ in a microwave reactor, and reacting for 120 min. A part of the obtained mixture was centrifuged, and the composition of the obtained liquid phase mixture was measured by gas chromatography to calculate that the conversion of propylene oxide was 88% and the selectivity of propylene glycol monomethyl ether was 90%.
Example 2:
adding 90mg of amino modified mesoporous nano-silica MCM-41 into 10mL of DMSO solution containing 40mg of succinic anhydride and 40mg of triethylamine, stirring for 48 hours at 40 ℃, centrifuging, and washing with ethanol to obtain the silicon carboxyl carrier.
80mg of the silicon oxide support is added into 6mL of aqueous solution containing 50mg of EDC and 20mg of NHS, and then 6mg of carbon dots containing amino groups on the surface are added at room temperature, stirred for 8 hours and centrifuged to obtain the composite catalyst for synthesizing the propylene glycol ether.
Adding the composite catalyst of the epoxy propane, the methanol and the synthetic propylene glycol ether into a microwave reaction tube, wherein the molar ratio of the epoxy propane to the methanol is 1: 7, the mass ratio of the composite catalyst to the propylene oxide is 1: 30. heating to 120 ℃ in a microwave reactor, and reacting for 120 min. A part of the obtained mixture was centrifuged, and the composition of the obtained liquid phase mixture was measured by gas chromatography to calculate that the conversion of propylene oxide was 70% and the selectivity of propylene glycol monomethyl ether was 80%.
Example 3:
2.5g of hexadecyltrimethylammonium bromideDissolving in 350mL of water, and sequentially adding 4mL of NH3H2O (30%), 75mL of diethyl ether and 25mL of ethanol, stirring uniformly, adding 12.5mL of ethyl orthosilicate and 0.5mL of 3-aminopropyltriethoxysilane, reacting for 4h at 20-25 ℃, adding 1mL of concentrated HCl to terminate the reaction, immediately centrifuging and washing, and drying to obtain the amino-modified mesoporous nano-silica spheres.
2.67g of alanine was dissolved in 30mL of ultrapure water, and then 0.8mL of ethylenediamine was added while stirring, and then the above solution was transferred to a 50mL high-temperature reaction tank and heated to 200 ℃. After 6 hours of reaction, the reaction mixture was cooled at room temperature, and the product was placed in a dialysis bag (1000MWCO), dialyzed for 48 hours, and freeze-dried to obtain the carbon dots having amino groups on the surface.
And adding 90mg of amino modified mesoporous nano-silica spheres into 10mL of DMSO solution containing 40mg of succinic anhydride and 40mg of triethylamine, stirring for 48 hours at 40 ℃, centrifuging, and washing with ethanol to obtain the carboxylated silicon carrier.
80mg of the carboxylated silicon carrier was added to 6mL of an aqueous solution containing 50mg of EDC and 20mg of NHS, and then 6mg of carbon dots containing amino groups on the surface were added at room temperature and stirred for 8 hours for centrifugation to obtain the composite catalyst for synthesizing propylene glycol ether, which is shown in FIG. 1 in a transmission electron microscope.
Adding the composite catalyst of the epoxy propane, the methanol and the synthetic propylene glycol ether into a microwave reaction tube, wherein the molar ratio of the epoxy propane to the methanol is 1:3, the mass ratio of the composite catalyst to the propylene oxide is 1: 100. heating to 120 ℃ in a microwave reactor, and reacting for 120 min. A part of the obtained mixture was centrifuged, and the composition of the obtained liquid phase mixture was measured by gas chromatography to calculate that the conversion of propylene oxide was 82% and the selectivity of propylene glycol monomethyl ether was 88%.
Example 4:
2.5g hexadecyl trimethyl ammonium bromide was added to 350mL of water, and after dissolution, 4mL of NH were added in sequence3H2O (30%), 75mL of diethyl ether and 25mL of ethanol, stirring uniformly, adding 12.5mL of ethyl orthosilicate and 0.5mL of 3-aminopropyltriethoxysilane, reacting for 4h at 20-25 ℃, finally adding 1mL of concentrated HCl to terminate the reaction, and immediately stopping the reactionAnd (4) centrifugally washing and drying to obtain the amino modified mesoporous nano silicon dioxide spheres.
2.67g of alanine was dissolved in 30mL of ultrapure water, and then 0.8mL of ethylenediamine was added while stirring, and then the above solution was transferred to a 50mL high-temperature reaction tank and heated to 200 ℃. After 6 hours of reaction, the reaction mixture was cooled at room temperature, and the product was placed in a dialysis bag (1000MWCO), dialyzed for 48 hours, and freeze-dried to obtain the carbon dots having amino groups on the surface.
And adding 90mg of amino modified mesoporous nano-silica spheres into 10mL of DMSO solution containing 40mg of succinic anhydride and 40mg of triethylamine, stirring for 48 hours at 40 ℃, centrifuging, and washing with ethanol to obtain the carboxylated silicon carrier.
80mg of the carboxylated silicon carrier was added to 6mL of an aqueous solution containing 50mg of EDC and 20mg of NHS, and then 6mg of carbon dots containing amino groups on the surface were added at room temperature and stirred for 8 hours for centrifugation to obtain the composite catalyst for synthesizing propylene glycol ether, which is shown in FIG. 1 in a transmission electron microscope.
Adding the composite catalyst of the epoxy propane, the methanol and the synthetic propylene glycol ether into a microwave reaction tube, wherein the molar ratio of the epoxy propane to the methanol is 1: 2, the mass ratio of the composite catalyst to the propylene oxide is 1: 10. heating to 120 ℃ in a microwave reactor, and reacting for 120 min. A part of the obtained mixture was centrifuged, and the composition of the obtained liquid phase mixture was measured by gas chromatography to calculate that the conversion of propylene oxide was 90% and the selectivity of propylene glycol monomethyl ether was 92%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the composite catalyst for synthesizing the propylene glycol ether is characterized by comprising the following steps of:
preparing amino modified mesoporous nano silicon dioxide spheres;
reacting the amino modified mesoporous nano silicon dioxide with succinic anhydride to obtain a carboxylated silicon carrier;
and carrying out condensation reaction on the carboxylated silicon carrier and carbon points with amino groups on the surface to obtain the composite catalyst for catalytically synthesizing propylene glycol ether.
2. The method for preparing a composite catalyst for synthesizing propylene glycol ether according to claim 1, wherein the diameter of the amino-modified mesoporous nano silica spheres is 200 to 400nm, and the mesoporous size is distributed between 4nm and 10 nm.
3. The method for preparing the composite catalyst for synthesizing propylene glycol ether according to claim 1, wherein the method for preparing the amino-modified mesoporous nano-silica spheres comprises the following steps: adding hexadecyl trimethyl ammonium bromide into water, sequentially adding ammonia water, diethyl ether and ethanol after dissolving, uniformly stirring, adding tetraethoxysilane and 3-aminopropyl triethoxysilane, reacting for 4 hours at 20-25 ℃, centrifuging, washing and drying to obtain the amino modified mesoporous nano-silica spheres.
4. The method for preparing a composite catalyst for synthesizing propylene glycol ether according to claim 1, wherein the carbon dots having amino groups on the surface are prepared by the steps of:
dissolving alanine, ethylenediamine and/or polyethyleneimine in water to obtain a mixed solution, wherein the mass ratio of the alanine to the ethylenediamine and/or polyethyleneimine is (1-4): 1;
and placing the mixed solution in a closed reaction container, heating to 180-240 ℃, keeping for 6-24 hours, cooling, and drying a product to obtain the carbon dots with the amino groups on the surface.
5. The method for preparing the composite catalyst for synthesizing propylene glycol ether according to claim 4, wherein the mass ratio of alanine to ethylenediamine and/or polyethyleneimine is 2-3: 1.
6. the method for preparing a composite catalyst for synthesizing propylene glycol ether according to claim 1, wherein the size of the carbon dots having amino groups on the surface is less than 5 nm.
7. The use of the composite catalyst for synthesizing propylene glycol ether according to claim 1 to 6 in the preparation of propylene glycol ether by catalyzing alcohol and propylene oxide.
8. The use of the composite catalyst of claim 7 for catalyzing an alcohol and propylene oxide to produce propylene glycol ether, wherein the alcohol is C1～C8Any one of alcohols.
9. The use of the composite catalyst of claim 7 in catalyzing alcohol and propylene oxide to prepare propylene glycol ether, wherein the composite catalyst is used in catalyzing alcohol and propylene oxide to prepare propylene glycol ether by feeding propylene oxide and alcohol into a reactor to contact with the nanocarbon point, and heating to 80-160 ℃ in a closed environment to obtain propylene glycol ether, wherein the mass ratio of the nanocarbon point to propylene oxide is 1: 10 to 500.
10. The use of the composite catalyst of claim 7 in catalyzing alcohol and propylene oxide to produce propylene glycol ether, wherein the mass ratio of the composite catalyst to propylene oxide is 1: 20 to 100.
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