CN110152704A - It is a kind of for synthetic linear carbonic ester without metal solid catalyst and preparation method thereof - Google Patents
It is a kind of for synthetic linear carbonic ester without metal solid catalyst and preparation method thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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Abstract
The invention belongs to solid catalyst preparation fields, and in particular to it is a kind of for synthetic linear carbonic ester without metal solid catalyst and preparation method thereof.The catalyst is with graphite phase carbon nitride (g-C3N4) it is raw material, it after being stripped, is handled through ammonium hydroxide, pyridine or the protonation of pyrroles, filtering, washing and drying and other steps obtain the g-C of deprotonation removing3N4Catalyst.The catalyst preparation is easy to operate, and no any metal ion introduces, and when being used for ethylene carbonate transesterification synthetic linear carbonic ester, catalyst activity is high, and recycling is simple and will not cause metal ion pollution to reaction product.
Description
Technical field
The invention belongs to the preparation fields of solid catalyst, and in particular to one kind is for ethylene carbonate and methanol or ethyl alcohol
Pass through the preparation method without metal solid catalyst of ester exchange reaction synthetic linear carbonic ester.
Background technique
It is a kind of widely used change with dimethyl carbonate (DMC), the linear carbonate that diethyl carbonate (DEC) is representative
Work raw material.Because linear carbonate is widely used in the organic synthesis such as being alkylated and be carbonylated containing there are many functional group, from
And substitute toxic dimethyl suflfate, methylchloroformate etc.；It can also be reacted with alcohol, ester and amino alcohol etc., synthetic resin,
The fine chemistry products such as insecticide, pesticide, food additives.DMC can substitute trichloro ethylene, benzene or dimethylbenzene etc. as paint
Coating, cleaning solvent etc..DMC and DEC is alternatively arranged as gasoline additive substituent methyl tertbutyl ether (MTBE), improve octane number and
Oxygen content, strengthen burning efficiency reduce the discharge amount of CO and nitrogenous compound.
The conventional method for industrially preparing linear carbonate mainly has phosgenation and oxidative carbonylation of methanol method.Phosgenation has
Severe toxicity is gradually eliminated.Oxidative carbonylation of methanol method is a kind of clean production using methanol, carbon monoxide and oxygen as raw material
Technique, but the yield that the method prepares linear carbonate is lower, and carbon monoxide is a kind of explosive, hypertoxic gas, there is peace
Full hidden danger.In contrast, ester-interchange method is a kind of novel production process for producing linear carbonate, it is with cyclic carbonate and alcohol
Class is raw material, is obtained by ester exchange reaction (such as formula 1).
Formula 1 is the reaction equation of the transesterification synthetic linear carbonic ester of cyclic carbonate.
Ester-interchange method is raw materials used to be easy to get, and low toxicity, at low cost, the corrosivity of equipment is small, the high income of DMC and DEC.In addition
The reaction process cleanliness without any pollution, belongs to environmentally friendly technique.By-product ethylene glycol is also important industrial chemicals simultaneously.Mesh
Before, China's most enterprises produce DMC and DEC using the above method.And the key problem of the technique is effective catalyst
Research and development.Currently, there are many catalyst system for the ester exchange reaction, highest activity is ionic liquid.Although ionic liquid
The catalytic activity of body is very high, but the biggest problems are that the catalysis reaction that ionic liquid participates in is homogeneous system, in product separation
Exist with purification aspect many difficult.(ACS the Applied Materials&Interfaces, 2013,5:9823-such as Sun Linbing
9829.) tert-butyl alcohol lithium is immobilized on mesoporous SBA-15, it is used to catalyzed transesterification.Watanabe etc.
(Microporous&Mesoporous Materials, 1998,22:399-407.) is with hydrotalcite type (Mg2.5Al-NO3) conduct
Catalyst is used for ester exchange reaction.Although above-mentioned solid catalyst overcomes the catalyst recycling problem after reaction, it is above-mentioned
Catalyst has the participation of metal salt, undoubtedly be easy to cause metal ion dirty the product (i.e. linear carbonate) of its transesterification
Dye.And on the other hand, when linear carbonate is applied to battery electrolyte, there is extremely harsh want to the content of its metal ion
It asks.
In recent years, graphite phase carbon nitride (g-C3N4) led as a kind of Novel non-metal material in heterogeneous catalysis, photocatalysis etc.
Domain causes the extensive concern of people.For the Nomenclature Composition and Structure of Complexes, g-C3N4Main unit is three s-triazine, in its class graphite linings
There are a large amount of amido functional groups at edge.Therefore g-C3N4It is a kind of typical solid alkali material.Using dicyanodiamine, melamine
The common g-C that amine or urea roasting direct obtain3N4Material specific surface is very low, and the base strength of material is very weak.If directly made
With common g-C3N4As catalyst, catalytic activity is lower.This seminar once reports g-C3N4The metal halide of load
It can be used for being catalyzed the ester exchange reaction synthetic linear carbonic ester (Chinese patent of cyclic carbonate ester with metal oxide materials
201410606485.9 with 201610415575.9).Although the introducing of metal halide and metal oxide can enhance g-C3N4's
Alkalinity finally improves its catalytic activity, but equally exists metal ion contamination problems.
Summary of the invention
The technical problem to be solved by the present invention is to face for used catalyst during current synthetic linear carbonic ester
Recycling difficulty and the problems such as metal ion pollution.
To solve the above-mentioned problems, the present invention is with g-C3N4For platform material, after baking first is carried out to it, removing is made
G-C3N4Material is carrying out deprotonation processing to it using ammonium hydroxide, pyridine or pyrroles, synthesized by removing and is going matter
Sonization without metal mold g-C3N4Catalyst, and applied and achieve positive reality during synthetic linear carbonic ester
Test effect.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
It is a kind of for synthetic linear carbonic ester without metal solid catalyst, the catalyst be after after baking is removed,
In the g-C handled through ammonium hydroxide, pyridine or pyrroles's deprotonation3N4Material.
Specifically making according to the following steps without metal solid catalyst for synthetic linear carbonic ester of the present invention
Standby.
(1) it using dicyanodiamine, melamine or urea organic amine as presoma, through 550 DEG C of 2-4h of roasting temperature, is made
g-C3N4Material.
(2) by step (1) g-C3N4After material grinding, continues to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4
Material (eg-C3N4)；
(3) by 0.5-1 mass parts eg-C3N4With 20 mass parts ammonium hydroxide, pyridine or chromium solution (0.1-2molL-1)
8-12h are quickly stirred under the conditions of 30-140 DEG C in autoclave；
(4) above-mentioned suspension is isolated to solid, be washed with water wash to pH be 7, then under the conditions of 80-120 DEG C do
It is dry overnight, it obtains for transesterification synthetic linear carbonic ester without metal g-C3N4Catalyst.
In the present invention, eg-C described in step (3)3N4Quality be preferably 0.6 mass parts；It is a length of when stirring preferred
10h；Deprotonation reagent is preferably ammonium hydroxide；Ammonia concn is preferably 0.3molL-1, preferably 120 DEG C of the temperature of alkali process.
In the present invention, drying temperature described in step (4) is preferably 100 DEG C.
Above-mentioned catalyst is used for methanol or ethyl alcohol and ethylene carbonate (EC) as raw material, synthetic linear carbonic ester, tool
The application method of body are as follows: the stainless steel equipped with temperature programmed control equipment and magnetic agitation that catalyst reaction equipment is 50-200mL is high
Press reaction kettle.Reaction condition is as follows: catalyst amount is 0.2 mass parts, and EC is 2.2 mass parts, and methanol or ethyl alcohol are 8 mass
Part, reaction temperature is 110-130 DEG C, and reaction filling gas is nitrogen, reaction time 4h.After reaction, reaction system passes through
Centrifuge separation.Experimental result is tested and analyzed using the gas-chromatography (SP6890) equipped with fid detector.
The following further describes the present invention with reference to the drawings.
Detailed description of the invention
Fig. 1 is the common g-C that dicyanodiamine, melamine or urea roasting direct obtain3N4Material and embodiment 1 are made
The N of standby CAT-1 catalyst2Adsorption and desorption isotherms.
Fig. 2 is common g-C3N4With the x-ray photoelectron spectroscopy figure of CAT-1.
Fig. 3 is g-C3N4Basic structural unit in the corresponding XPS spectrum of difference N species combination can scheme.
Specific embodiment
The present invention will be described further with regard to following embodiment, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the limitation that the present invention is implemented.
Embodiment 1
Using dicyanodiamine as presoma, through 550 DEG C of roasting temperature 3h, g-C is made3N4Material.By above-mentioned g-C3N4Material
After grinding, continues to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4Material eg-C3N4.By 0.6 mass parts eg-C3N4With
Ammonium hydroxide (the 0.3molL of 20 mass parts-1) be added in autoclave.10h is stirred to react at 120 DEG C.After reaction
It is separated, being washed with water to wash to pH to be dried overnight for 7,100 DEG C can be obtained for synthetic linear carbonic ester without metal solid
Catalyst CAT-1.
Fig. 1 is the common g-C that dicyanodiamine, melamine or urea roasting direct obtain3N4Material and embodiment 1 are made
The N of standby CAT-1 catalyst2Adsorption and desorption isotherms.Common g-C3N4To N2Adsorbance it is very low, and CAT-1 in contrast its
Adsorbance has significant raising.This illustrates CAT-1 than common g-C3N4With richer pore structure.According to BET equation calculation
Common g-C out3N4Specific surface area with CAT-1 is respectively 9 and 85m2g-1, further illustrate the latter's specific surface with higher
's.In heterogeneous catalytic reaction, higher specific surface is conducive to the more active sites of catalyst exposure, therefore can improve its catalysis
Activity.
Fig. 2 is common g-C3N4With the x-ray photoelectron spectroscopy figure of CAT-1.The N 1s trajectory diagram can analyze nitrogen member in catalyst
The bonding pattern and content of element.Wherein combination can correspond respectively to g-C for 398.5,399.4 and 401.1eV3N4In three s-triazine
Middle sp2The nitrogen (Fig. 3) of the nitrogen of hydridization, the nitrogen of three s-triazine of bridging and class graphite linings edge.Wherein the first nitrogen is without alkalinity.And the
The alkalinity of two kinds of nitrogen is much higher than a kind of last alkalinity of nitrogen.It therefore is catalytic active site in the base catalyzed reactions such as transesterification.Fig. 2
Peak integral calculation analysis known to: second of nitrogen is in common g-C3N4It is respectively 22% and 34% with the content in CAT-1.Into one
The catalytic activity that step proves catalyst of the invention is higher than common g-C3N4Material.
Embodiment 2
Using melamine as presoma, through 550 DEG C of roasting temperature 2h, g-C is made3N4Material.By above-mentioned g-C3N4Material
After grinding, continues to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4Material eg-C3N4.By the eg-C of 0.5 mass parts3N4
With the ammonium hydroxide (0.1molL of 20 mass parts-1) be added in autoclave.8h is stirred to react at 30 DEG C.After reaction
It is separated, is washed with water to wash and is 7,80 DEG C to pH and is dried overnight and can be obtained urging without metal solid for synthetic linear carbonic ester
Agent CAT-2.
Embodiment 3
Using urea as presoma, through 550 DEG C of roasting temperature 4h, g-C is made3N4Material.By above-mentioned g-C3N4Material grinding
Afterwards, continue to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4Material eg-C3N4.By the eg-C of 1 mass parts3N4With 20 matter
Measure the ammonium hydroxide (2molL of part-1) be added in autoclave.12h is stirred to react at 140 DEG C.After reaction through separating,
Being washed with water to wash to pH to be dried overnight for 7,120 DEG C can be obtained for synthetic linear carbonic ester without metal solid catalyst
CAT-3。
Embodiment 4
Using dicyanodiamine as presoma, through 550 DEG C of roasting temperature 3h, g-C is made3N4Material.By above-mentioned g-C3N4Material
After grinding, continues to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4Material eg-C3N4.By the eg-C of 0.6 mass parts3N4
With the ammonium hydroxide (1molL of 20 mass parts-1) be added in autoclave.10h is stirred to react at 90 DEG C.It passes through after reaction
Separation, being washed with water to wash to be dried overnight to pH for 7,90 DEG C can be obtained for synthetic linear carbonic ester without metal solid catalysis
Agent CAT-4.
Embodiment 5
Using dicyanodiamine as presoma, through 550 DEG C of roasting temperature 3h, g-C is made3N4Material.By above-mentioned g-C3N4Material
After grinding, continues to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4Material eg-C3N4.By the eg-C of 0.8 mass parts3N4
It is added to the pyrroles (0.3molL of 20 mass parts-1) be added in autoclave.10h is stirred at 120 DEG C.Reaction terminates
By separation, being washed with water to wash to be dried overnight to pH for 7,100 DEG C be can be obtained for the solid without metal of synthetic linear carbonic ester
Body catalyst CAT-5.
Embodiment 6
Using dicyanodiamine as presoma, through 550 DEG C of roasting temperature 3h, g-C is made3N4Material.By above-mentioned g-C3N4Material
After grinding, continues to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4Material eg-C3N4.By the eg-C of 0.6 mass parts3N4
It is added to the pyridine (0.3molL of 20 mass parts-1) be added in autoclave.10h is stirred at 120 DEG C.Reaction terminates
By separation, being washed with water to wash to be dried overnight to pH for 7,100 DEG C be can be obtained for the solid without metal of synthetic linear carbonic ester
Body catalyst CAT-6.
Comparative example 1
Using dicyanodiamine as presoma, through 550 DEG C of roasting temperature 3h, g-C is made3N4Material.By above-mentioned g-C3N4Material
After grinding, continues to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4Material (eg-C3N4), and it is used for synthetic thread
Type carbonic ester without metal solid catalyst D-CAT-1.
Comparative example 2
Using dicyanodiamine as presoma, through 550 DEG C of roasting temperature 3h, g-C is made3N4Material.0.6 mass parts are above-mentioned
g-C3N4Ammonium hydroxide (the 0.3molL of material and 20 mass parts-1) be added in autoclave.It is stirred to react at 120 DEG C
10h.It is separated after reaction, being washed with water to wash to pH to be dried overnight for 7,100 DEG C can be obtained for synthetic linear carbonic acid
Ester without metal solid catalyst D-CAT-2.
Transesterification synthetic linear carbonic ester evaluating catalyst condition:
Above-mentioned catalyst is applied to using DMC as in the synthetic reaction of the linear carbonate of representative.Reaction condition is as follows: urging
Agent dosage is 0.2 mass parts, and EC is 2.2 mass parts, and methanol or ethyl alcohol are 8 mass parts, and reaction temperature is 110-130 DEG C, instead
Answering filling gas is nitrogen, reaction time 4h.After reaction, reaction system is centrifuged.Using equipped with fid detector
Gas-chromatography (SP6890) test and analyze experimental result.Concrete outcome is as shown in table 1.
The various catalyst of table 1 are in EC and CH3OH (or C2H5OH) the catalytic activity of ester exchange reaction
After reaction, it is washed through deionized water and dehydrated alcohol, the catalysis up to recycling is dried overnight at 100 DEG C
Agent.Catalyst CAT-1 is in EC and CH3Repeat performance in the transesterification synthesis DMC of OH is as shown in table 2.
2 catalyst CAT-1 of table is in EC and CH3The recycling performance of OH ester exchange reaction
From table 2 it can be seen that the conversion ratio of EC and the yield of DMC are basic after the catalyst is recycled by four times
Stablize, illustrates that the catalyst may be reused.
Claims (6)
1. it is a kind of for synthetic linear carbonic ester without metal solid catalyst, which is characterized in that the catalyst be by stripping
From rear, then the g-C through ammonium hydroxide, pyridine or pyrroles's deprotonation3N4Catalyst is free of metal or metal ion component.
2. the preparation method without metal solid catalyst according to claim 1 for synthetic linear carbonic ester, special
Sign is that specific step is as follows for the preparation method:
(1) using dicyanodiamine, melamine or urea as presoma, 2-4h are roasted at 550 DEG C, and g-C is made3N4Material；
(2) by step (1) resulting g-C3N4After material grinding, continues to roast 2h under the conditions of 550 DEG C, the g-C of removing is made3N4
Material, i.e. eg-C3N4；
(3) by eg-C3N48-12h are stirred at 30-140 DEG C with ammonium hydroxide, pyridine or chromium solution, obtain suspension；
(4) suspension that step (3) obtains is isolated to solid, be washed with water wash to pH be 7, then in 80-120 DEG C of items
It is dried overnight under part to get arriving for transesterification synthetic linear carbonic ester without metal g-C3N4Catalyst.
3. the preparation method without metal solid catalyst according to claim 2 for synthetic linear carbonic ester, special
Sign is, step (3) described eg-C3N4With the mass ratio of ammonium hydroxide, pyridine or chromium solution are as follows: 0.5-1:20, ammonium hydroxide, pyridine or
The concentration of chromium solution is 0.1-2molL-1。
4. the preparation method without metal solid catalyst according to claim 2 for synthetic linear carbonic ester, special
Sign is, step (3) is by the eg-C of 0.6 mass parts3N410h is stirred at 120 DEG C with the ammonium hydroxide of 20 mass parts, obtains suspension；
The ammonia concn is 0.3molL-1。
5. a kind of application without metal solid catalyst according to claim 1 for synthetic linear carbonic ester, special
Sign is that the catalyst is used for methanol or ethyl alcohol and ethylene carbonate (EC) as raw material, synthetic linear carbonic ester.
6. the application method without metal solid catalyst according to claim 5 for synthetic linear carbonic ester, special
Sign is, the application method specifically: it according to methanol or ethyl alcohol is 8 mass parts, EC is the raw material dosage of 2.2 mass parts,
Be added 0.2 mass parts without metal solid catalyst, be 110-130 DEG C in reaction temperature, reaction filling gas is the item of nitrogen
4h, synthetic linear carbonic ester are reacted under part.
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| CN114210273A (en) * | 2021-12-24 | 2022-03-22 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
| 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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| 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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