CN104383951A - Catalyst for synthesis of linear carbonate by virtue of transesterification of cyclic carbonate and alcohol and preparing method of catalyst - Google Patents
Catalyst for synthesis of linear carbonate by virtue of transesterification of cyclic carbonate and alcohol and preparing method of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesis of linear carbonate by virtue of transesterification of cyclic carbonate and alcohol and a preparing method of the catalyst. The catalyst is prepared by taking carbon nitride as a carrier and using transition metal halide ZnBr2, ZnCl2, FeCl3, NiCl2 or CoCl2 as an active component. The catalyst can be successfully applied to synthesis of linear carbonate by virtue of transesterification of cyclic carbonate and alcohol, and is capable of efficiently catalyzing ethylene carbonate; the preparing method of the catalyst is simple and convenient and short in period, raw materials are cheap and easily available, and the reuse effect of the catalyst is good.
Description
Technical field
The invention belongs to heterogeneous catalysis field, be specifically related to a kind of Catalysts and its preparation method for cyclic carbonate and alcohol transesterification reaction synthetic linear carbonic ester.
Background technology
With dimethyl carbonate, the chemical intermediate that diethyl carbonate to be the linear carbonate of representative a be class is important.Because its toxicity is low, easily biological-degradable, meets the environmental requirement of chemical products.Containing multiple functional group in the molecular structure of linear carbonate, the reactions such as the dimethyl suflfate photoreactive gas of severe toxicity carries out methylating, carbonylation can be replaced, thus have a wide range of applications in fields such as plastics, dyestuff, food additives, medicine and agricultural chemicals, and be considered to the green basic chemical industry raw material of 21 century and the new matrix (building block) of organic synthesis.In addition, linear carbonate or a kind of good organic solvent, and can be used for gasoline additive to improve its octane number.
Since Hood and Murdock in 1918 obtains dimethyl carbonate with phosgene and Methanol first, develop the method for several synthetic linear carbonic ester successively, as phosgenation, oxidative carbonylation of methanol method and ester-interchange method.Phosgenation is eliminated substantially because using the phosgene of severe toxicity.Oxidative carbonylation of methanol method for raw material, be a kind of clean production technology, but the productive rate that the method prepares linear carbonate is lower with methyl alcohol, carbon monoxide and oxygen, and carbon monoxide is explosive, hypertoxic gas, there is serious potential safety hazard.By contrast, by a kind of novel production process that cyclic carbonate (as ethylene carbonate, propene carbonate) and lower aliphatic alcohols (as methyl alcohol) ester-interchange method are production of linear carbonic esters, it, is obtained by ester exchange reaction (being shown below) for raw material with cyclic carbonate and lower aliphatic alcohols.
Wherein, R
1=H, CH
3; R
2=CH
3, C
2h
5.
The raw materials used low toxicity of this generating process, in addition, accessory substance ethylene glycol or propane diols are also important industrial chemicals.Therefore, carrying out synthetic linear carbonic ester with the ester-interchange method of cyclic carbonate ester is clean, a continuable synthetic route.
Ester exchange reaction due to cyclic carbonate ester is the reaction that chemical kinetics controls, and often needs to add catalyst to improve its reaction rate, Reaction time shorten in actual synthesis.At present, the catalyst system for this ester exchange reaction is a lot, and what its activity was the highest is ionic liquid.He Liangnian etc. (Tetrahedron Letters, 2010,51,2931.) alkali ionic liquid [C
4dABCO] OH is used for the ester exchange reaction of ethylene carbonate (10mmol) and methyl alcohol (150mmol) as catalyst, catalyst amount 18.7mg, after 70 DEG C of reaction 6h, the conversion ratio of ethylene carbonate is 90%, and the productive rate of dimethyl carbonate is 81%.(the Speciality Petrochemicals such as Ma Chengming, 2012,6,58.) ester exchange reaction of dimethyl carbonate and methyl alcohol is used for using 1-butyl-3-methylimidazole hydroxide as catalyst, at reaction time 4h, temperature is 67 DEG C, catalyst 0.3g, under the condition that alcohol ester ratio is 10:1, the conversion ratio of ethylene carbonate and the selective respectively up to 88.5% and 90.3% of dimethyl carbonate.Zhang Suojiang etc. (Chinese patent CN 102126957A) are in 100mL stainless steel cauldron, add catalyst butyl pyridinium chloride 1.2mmol, ethylene carbonate 10.5g (0.12mol) and methyl alcohol 38mL (0.96mol), closed reactor, reaction temperature 140 DEG C, pressure is 0.3MPa, reaction 1h, ethylene carbonate ester conversion rate is 72%, and the selective of dimethyl carbonate is 99%.
Although the catalytic activity of ionic liquid is very high, maximum problem is that the catalytic reaction that ionic liquid participates in is homogeneous system, there is a lot of difficulty in product separation and purification.In addition, report is also had to use the ester exchange reaction of catalyzed by solid base linear carbonates and alcohol.(the petrochemical industry such as Wei Tong, 2002,12,959.) by equi-volume impregnating, KOH is loaded in mesoporous carbon, at 120 DEG C, the molar ratio of propene carbonate and methyl alcohol is 1:6, in autoclave, react 2h, the conversion ratio of propene carbonate is 32.4%, and the yield of dimethyl carbonate is 29.1%.Sun Linbing etc. (Chinese patent CN 102698811A) by immobilized for tert-butyl alcohol lithium on mesoporous SBA-15, be used for catalyzed transesterification, wherein methyl alcohol 20mL, ethylene carbonate 8.7076g, catalyst 0.079g, 60 DEG C of reaction 4h in flask, the productive rate of dimethyl carbonate is 41.0%.Although these solid catalysts overcome post catalyst reaction well and reclaim problem, there is catalysis general activity not high, the shortcomings such as poor stability.
Graphite phase carbon nitride (g-C
3n
4) material is a kind of carbonitride covalent compound of novel class graphite laminate structure.Because it has lower energy gap (~ 2.7eV), higher heat endurance and the capacity of heat transmission, special optics and energy storage character, be widely used in the field such as fuel cell and light-catalyzed reaction.G-C
3n
4main unit is three s-triazine, at the amine species that its class graphite linings marginal existence is a large amount of.Therefore, as the typical solid base of one, g-C
3n
4energy catalysis Knoevenagel condensation, the organic reaction of the multiple base catalysis such as 'beta '-ketoester exchange.This seminar (Catalysis Science & Technology, 2013,3,3192.) reported and used mesoporous carbonitride catalyzed carbon vinyl acetate and methyl alcohol ester exchange Synthesis of dimethyl carbonate.Although mesoporous carbonitride shows good catalytic activity to this catalytic reaction, but the synthetic method of this catalyst relates to the preparation of hard template (i.e. meso pore silicon oxide material), a series of processes such as the perfusion of presoma and stripper plate, manufacturing cycle reaches about 2 weeks, and cost higher (needing expensive non-ionic surface active agent).Given this, be necessary to develop that a kind of manufacturing cycle is short, cheaper starting materials, active high carbon nitride catalyst is used for cyclic carbonate and alcohol ester exchange synthetic linear carbonic ester.
Summary of the invention
The technical problem to be solved in the present invention is the problems such as, poor stability complicated, expensive for the current method for preparing catalyst for cyclic carbonate and alcohol transesterification reaction, provides a kind of carbonitride carrying transition metal halide type solid catalyst.This catalyst has higher catalytic activity and product yield, and it is simple and reuse effective that reaction terminates rear separation.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Catalyst of the present invention is carrier with carbonitride, take transition metal halide as active component; Wherein said transition metal halide is ZnBr
2, ZnCl
2, FeCl
3, NiCl
2or CoCl
2in one, wherein preferred ZnBr
2.
The above-mentioned catalyst its preparation method of the present invention carries out according to following steps:
(1) by the transition metal halide of 0.015 – 0.07 mass parts, the methyl alcohol of 20 – 30 mass parts or the dicyanodiamine of ethanol and 4 mass parts or melamine mixing, in 50 –, 60 DEG C of lower open mouth heating, drying is stirred to;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 3 – 6h at 550 DEG C, can obtain described catalyst.
The catalyst application that the present invention is obtained in the ester exchange reaction of cyclic carbonate and alcohol, concrete reaction condition and step as follows:
(1) by the cyclic carbonate of 20 – 25 mass parts and the alcohol of 80 mass parts, the catalyst of 1 mass parts is added in autoclave, and 140 – 160 DEG C react 3 – 8h;
(2) centrifugation catalyst after completion of the reaction.Product is through gas chromatographic analysis, and the conversion ratio of cyclic carbonate is 45 – 84%, and the selective of linear carbonate is 71 – 99%, and the productive rate of linear carbonate is 43 – 83%.
Wherein, described cyclic carbonate is ethylene carbonate or propene carbonate, wherein preferred ethylene carbonate; The described alcohol reacted with cyclic carbonate is low molecular methyl alcohol or ethanol, wherein particular methanol.In the reaction condition of this ester exchange reaction: wherein preferred reaction temperature is 160 DEG C, and the preferred reaction time is 4h.
After adopting technique scheme, the present invention, compared with the conventional catalyst such as ion exchange resin, ionic liquid, mesoporous carbonitride, has the following advantages:
(1) carbonitride carrying transition metal halide type catalyst of the present invention is a kind of solid catalyst, after reaction terminates, after simple Separation of Solid and Liquid, can reuse.
(2) carbonitride carrying transition metal halide type catalyst preparing extremely simple (only needing mixing-drying-roasting three step), manufacturing cycle is 1 – 2 days.Raw materials used i.e. dicyanodiamine (or melamine) and transition metal halide low toxicity, inexpensive, easy industrial applications.
(3) catalytic activity and product yield higher, wherein the conversion ratio of cyclic carbonate can reach 84%, and the selective of linear carbonate reaches as high as 99%, and the productive rate of carbonic ester is for reaching as high as 83%.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is the X-ray diffractogram (XRD) of embodiment 1 catalyst.As figure, place's appearance high strength in 2 θ=27.5 ° and sharp-pointed diffraction maximum.The interlayer that this peak belongs to class graphite piles up (interplanarstacking), its interlamellar spacing d
(002)=0.325nm.In addition, in 2 θ=12.7, also there is more weak diffraction maximum at a ° place.The document that contrast carbon nitride material is relevant, accumulation (in-planestacking) in the face that this peak can belong to class graphite linings, its interlamellar spacing d
(100)=0.696nm.The above results shows: this catalyst is the carbon nitride material of graphite-like structure.Attention: because active component content is low, and decentralization is higher, XRD cannot detect ZnBr
2species.
Fig. 2 is the x-ray photoelectron spectroscopy (XPS) of embodiment 2 catalyst.As shown in the figure, the fingerprint peaks of C, N and O element is detected at combination energy 288eV, 399eV and 533eV place.Wherein O element is the Interference Peaks that in air, a small amount of hydrone causes.Meanwhile, the fingerprint peaks of Br and Zn is detected at combination energy 88eV and 1023eV place.By upper explanation, this catalyst main component is the carbonitride of C and N, containing a small amount of ZnBr
2.Namely carbonitride is carrier, ZnBr
2for active component.
Detailed description of the invention
The present invention will be described further with regard to following examples, but it is to be understood that these embodiments are only the use illustrated, and should not be interpreted as restriction of the invention process.
Embodiment 1
(1) by the ZnBr of 0.015 mass parts
2, the methyl alcohol of 20 mass parts and 4 mass parts dicyanodiamine mixing, 50 DEG C of lower open mouths heating, be stirred to dry;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 4h at 550 DEG C, obtains catalyst sample;
(3) by the methyl alcohol of the ethylene carbonate of 22 mass parts and 80 mass parts, the catalyst of 1 mass parts is added in autoclave, 140 DEG C of reaction 8h;
(4) react complete, centrifugation catalyst, product is through gas chromatographic analysis: the conversion ratio of ethylene carbonate is 45%, and the selective of dimethyl carbonate is 95%, and the productive rate of dimethyl carbonate is 43%.
Embodiment 2
(1) by the ZnBr of 0.05 mass parts
2, the ethanol of 25 mass parts and 4 mass parts dicyanodiamine mixing, 60 DEG C of lower open mouths heating, be stirred to dry;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 4h at 550 DEG C, obtains catalyst sample;
(3) by the methyl alcohol of the ethylene carbonate of 22 mass parts and 80 mass parts, the catalyst of 1 mass parts is added in autoclave, 160 DEG C of reaction 3h;
(4) react complete, centrifugation catalyst, product is through gas chromatographic analysis, and the conversion ratio of ethylene carbonate is 64%, and the selective of dimethyl carbonate is 97%, and the productive rate of dimethyl carbonate is 62%.
Embodiment 3
(1) by the ZnBr of 0.05 mass parts
2with the ethanol of 25 mass parts, the melamine mixing of 4 mass parts, 55 DEG C of lower open mouth heating, is stirred to dry;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 4h at 550 DEG C, obtains catalyst sample;
(3) by the methyl alcohol of the ethylene carbonate of 22 mass parts and 80 mass parts, the catalyst of 1 mass parts is added in autoclave, 160 DEG C of reaction 4h;
(4) react complete, centrifugation catalyst, product is through gas chromatographic analysis, and the conversion ratio of ethylene carbonate is 84%, and the selective of dimethyl carbonate is 99%, and the productive rate of dimethyl carbonate is 83%.
Embodiment 4
(1) by the ZnBr of 0.05 mass parts
2, the methyl alcohol of 30 mass parts and 4 mass parts dicyanodiamine mixing, 60 DEG C of lower open mouths heating, be stirred to dry;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 3h at 550 DEG C, obtains catalyst sample;
(3) by the ethanol of the ethylene carbonate of 22 mass parts and 80 mass parts, the catalyst of 1 mass parts is added in autoclave, 160 DEG C of reaction 8h;
(4) react complete, centrifugation catalyst, product is through gas chromatographic analysis, and the conversion ratio of ethylene carbonate is 60%, and the selective of diethyl carbonate is 71%, and the productive rate of diethyl carbonate is 43%.
Embodiment 5
(1) by the ZnCl of 0.05 mass parts
2, the methyl alcohol of 20 mass parts and 4 mass parts dicyanodiamine mixing, 50 DEG C of lower open mouths heating, be stirred to dry;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 4h at 550 DEG C, obtains catalyst sample;
(3) by the methyl alcohol of the ethylene carbonate of 22 mass parts and 80 mass parts, the catalyst of 1 mass parts is added in autoclave, 160 DEG C of reaction 4h;
(4) react complete, centrifugation catalyst, product is through gas chromatographic analysis, and the conversion ratio of ethylene carbonate is 73%, and the selective of dimethyl carbonate is 98%, and the productive rate of dimethyl carbonate is 72%.
Embodiment 6
(1) by the FeCl of 0.05 mass parts
3, the ethanol of 25 mass parts and 4 mass parts melamine mixing, 60 DEG C of lower open mouths heating, be stirred to dry;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 5h at 550 DEG C, obtains catalyst sample;
(3) by the ethanol of the propene carbonate of 20 mass parts and 80 mass parts, the catalyst of 1 mass parts is added in autoclave, 150 DEG C of reaction 8h;
(4) react complete, centrifugally obtain catalyst, product is through gas chromatographic analysis, and the conversion ratio of propene carbonate is 76%, and the selective of diethyl carbonate is 88%, and the productive rate of diethyl carbonate is 67%.
Embodiment 7
(1) by the CoCl of 0.05 mass parts
2, the ethanol of 25 mass parts and 4 mass parts dicyanodiamine mixing, 160 DEG C of lower open mouths heating, be stirred to dry;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 4h at 550 DEG C, obtains catalyst sample;
(3) methyl alcohol of the propene carbonate of 25 mass parts, 80 mass parts and the catalyst of 1 mass parts are added in autoclave, 160 DEG C of reaction 6h;
(4) react complete, centrifugation catalyst, product is through gas chromatographic analysis, and the conversion ratio of propene carbonate is 71%, and the selective of dimethyl carbonate is 85%, and the productive rate of dimethyl carbonate is 60%.
Embodiment 8
(1) by the NiCl of 0.07 mass parts
2, the ethanol of 30 mass parts and 4 mass parts dicyanodiamine mixing, 160 DEG C of lower open mouths heating, be stirred to dry;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 4h at 550 DEG C, obtains catalyst sample;
(3) methyl alcohol of the ethylene carbonate of 20 mass parts, 80 mass parts and the catalyst of 1 mass parts are added in autoclave, 160 DEG C of reaction 4h;
(4) react complete, centrifugation catalyst, product is through gas chromatographic analysis, and the conversion ratio of ethylene carbonate is 75%, and the selective of dimethyl carbonate is 98%, and the productive rate of dimethyl carbonate is 74%.
The catalyst ethylene carbonate used in the embodiment of the present invention 3 and methyl alcohol ester exchange Synthesis of dimethyl carbonate are reused, to test its reusable performance, concrete outcome is in table 1.
The repeat performance of catalyst in table 1 embodiment 3
As can be seen from Table 1, after reusing through four times, catalyst still can remain on more than 80% to the conversion ratio of dimethyl carbonate, selective, remains on 99%.Illustrate that this catalyst has good reusability.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to right.
Claims (3)
1., for a catalyst for cyclic carbonate and alcohol transesterification reaction synthetic linear carbonic ester, it is characterized in that this catalyst is is carrier with carbonitride, take transition metal halide as active component.
2. a kind of catalyst for cyclic carbonate and alcohol transesterification reaction synthetic linear carbonic ester according to claim 1, is characterized in that described transition metal halide is ZnBr
2, ZnCl
2, FeCl
3, NiCl
2or CoCl
2.
3. the preparation method of a kind of catalyst for cyclic carbonate and alcohol transesterification reaction synthetic linear carbonic ester according to claim 1, is characterized in that what the method was specifically carried out according to following steps:
(1) by the transition metal halide of 0.015 – 0.07 mass parts, the methyl alcohol of 20 – 30 mass parts or the dicyanodiamine of ethanol and 4 mass parts or melamine mixing, in 50 –, 60 DEG C of lower open mouth heating, drying is stirred to;
(2) above-mentioned solid is placed in Muffle furnace, in airtight crucible, roasting 3 – 6h at 550 DEG C, can obtain described catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536838A (en) * | 2015-12-03 | 2016-05-04 | 湖南凯美特气体股份有限公司 | Preparation method of acid-alkali bi-functionalized C3N4 catalyst and cyclic carbonic ester |
| CN106588658A (en) * | 2016-11-18 | 2017-04-26 | 常州大学 | Method of synthesizing dimethyl carbonate |
| CN108499592A (en) * | 2018-05-07 | 2018-09-07 | 常州大学 | One kind being used for CO2Catalyst of cycloaddition reaction and preparation method thereof |
| CN106076387B (en) * | 2016-06-14 | 2019-03-22 | 常州大学 | A kind of application of heterogeneous catalyst in cyclic carbonate and alcohol transesterification synthetic linear carbonic ester |
| CN112156799A (en) * | 2020-09-10 | 2021-01-01 | 中国科学院山西煤炭化学研究所 | For CO2Catalyst for cycloaddition reaction, preparation method and application thereof |
| CN114931964A (en) * | 2022-05-18 | 2022-08-23 | 扬州大学 | B doping with g-C 3 N 4 Application of catalyst in catalytic synthesis of dimethyl carbonate |
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| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
Non-Patent Citations (1)
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| MOHD BISMILLAH等: "CO2 activation and promotional effect in the oxidation of cyclic olefins over mesoporous carbon nitrides", 《GREEN CHEMISTRY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536838A (en) * | 2015-12-03 | 2016-05-04 | 湖南凯美特气体股份有限公司 | Preparation method of acid-alkali bi-functionalized C3N4 catalyst and cyclic carbonic ester |
| CN105536838B (en) * | 2015-12-03 | 2018-06-19 | 湖南凯美特气体股份有限公司 | Soda acid difunctionalization C3N4The preparation method of catalyst and cyclic carbonate |
| CN106076387B (en) * | 2016-06-14 | 2019-03-22 | 常州大学 | A kind of application of heterogeneous catalyst in cyclic carbonate and alcohol transesterification synthetic linear carbonic ester |
| CN106588658A (en) * | 2016-11-18 | 2017-04-26 | 常州大学 | Method of synthesizing dimethyl carbonate |
| CN108499592A (en) * | 2018-05-07 | 2018-09-07 | 常州大学 | One kind being used for CO2Catalyst of cycloaddition reaction and preparation method thereof |
| CN112156799A (en) * | 2020-09-10 | 2021-01-01 | 中国科学院山西煤炭化学研究所 | For CO2Catalyst for cycloaddition reaction, preparation method and application thereof |
| CN112156799B (en) * | 2020-09-10 | 2021-11-09 | 中国科学院山西煤炭化学研究所 | For CO2Catalyst for cycloaddition reaction, preparation method and application thereof |
| CN114931964A (en) * | 2022-05-18 | 2022-08-23 | 扬州大学 | B doping with g-C 3 N 4 Application of catalyst in catalytic synthesis of dimethyl carbonate |
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