CN106588658B - Method for synthesizing dimethyl carbonate - Google Patents
Method for synthesizing dimethyl carbonate Download PDFInfo
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- CN106588658B CN106588658B CN201611028332.6A CN201611028332A CN106588658B CN 106588658 B CN106588658 B CN 106588658B CN 201611028332 A CN201611028332 A CN 201611028332A CN 106588658 B CN106588658 B CN 106588658B
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- graphene oxide
- ethylene carbonate
- dimethyl carbonate
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 28
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 28
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 carbon nanotube modified graphene Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing dimethyl carbonate, which takes graphene oxide modified by carbon nano tubes as a catalyst, takes ethylene carbonate and methanol as raw materials, and is carried out in a high-pressure kettle at a certain temperature and pressure.
Description
Technical Field
The invention relates to the field of synthesis of dimethyl carbonate, in particular to a method for synthesizing dimethyl carbonate by using a carbon nano tube modified by graphene oxide as a catalyst.
Background
Dimethyl Carbonate (DMC) is a colorless, transparent, slightly odorous, slightly sweet liquid at room temperature, is poorly soluble in water, but is miscible with almost all organic solvents such as alcohols, ethers, ketones, and the like. DMC is very low in toxicity, is listed as a non-toxic product in Europe in 1992, and is an environment-friendly chemical raw material meeting the requirements of modern cleaning processes, so that the DMC synthesis technology is widely regarded by the chemical industry at home and abroad.
The initial method of DMC production was the phosgene process, which was successfully developed in 1918, but the toxicity and corrosiveness of phosgene have limited the use of this process, and particularly the phosgene process has been eliminated as environmental protection has become increasingly important worldwide.
The synthesis of dimethyl carbonate by transesterification of ethylene carbonate with methanol is currently the most common route used by the industry. The catalytic system of the ester exchange reaction can be divided into homogeneous catalytic reaction and heterogeneous catalytic reaction, at present, DMC synthesized at home and abroad mainly passes through the homogeneous catalytic reaction system, and the catalysts used in the reaction comprise: alkali metal oxides, alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, alkali metal oxalates, quaternary ammonium halides, organic bases, and the like. The catalyst used in the industrial synthesis of dimethyl carbonate from propylene carbonate and methanol is sodium methoxide, but the use of sodium methoxide catalyst has many disadvantages, which can be summarized as follows: (1) the dosage of the catalyst is large, and about 80-110kg of sodium methoxide with the mass percentage of 25-30% is needed for producing 1 ton of dimethyl carbonate industrially at present; (2) a large amount of waste residues are generated after the catalyst is invalid, so that the environmental pollution is caused; (3) the precipitation of solids in the catalytic system affects the stability of continuous production of the system, blocks pipelines and equipment and seriously affects the continuity of production; (4) the forming process is complex, in order to remove the catalyst waste residue from a reaction material system and prevent solid waste from being separated out during rectification, the solid waste is attached to the inner wall surface of a heat exchanger tube nest and attached to a filler, desalted water and introduced carbon dioxide are added into heavy components discharged from a tower kettle of a reaction rectification tower so as to ensure that residual catalyst sodium methoxide loses efficacy and becomes sodium hydroxide, then the sodium hydroxide reacts with the carbon dioxide and becomes inorganic salt sodium carbonate, and then the sodium carbonate is filtered out through a filter, so that the production process is very complex; (5) the catalyst can not be recycled, and the catalyst has no catalytic action because the catalyst generates sodium carbonate inorganic salt after being out of service.
Therefore, it is significant to develop a method for synthesizing dimethyl carbonate, which has the advantages of simple operation, convenient separation of products and catalysts, high purity of obtained products, and good catalyst recovery and reuse performance. However, the synthesis of dimethyl carbonate by using graphene oxide as a catalyst has not been reported in the literature so far.
Disclosure of Invention
The invention aims to solve the technical problems of large catalyst usage amount, difficult catalyst separation and recovery, low yield of the product dimethyl carbonate and the like in the process of synthesizing the dimethyl carbonate by the exchange of ethylene carbonate and methanol, and provides the method for synthesizing the dimethyl carbonate, which has the advantages of simple operation, high catalyst efficiency, convenient product and catalyst separation, and good catalyst recovery and reuse performance.
In order to solve the problems, the invention adopts the following technical scheme:
the DMC synthesis method takes carbon nano tube modified graphene oxide as a catalyst, takes ethylene carbonate and methanol as raw materials, and carries out reaction in a high-pressure kettle.
The carbon nanotube modified graphene oxide catalyst is prepared by the following method: adding graphene oxide and carbon nanotubes into deionized water, performing ultrasonic treatment at room temperature for 2h, wherein the mass concentration of the graphene oxide in the deionized water is 1%, and then filtering and drying, wherein the mass ratio of the graphene oxide to the carbon nanotubes is 1:1-4: 1.
The synthesis of dimethyl carbonate was carried out as follows: adding a certain amount of methanol, ethylene carbonate and carbon nano tube modified graphene oxide into a high-pressure reaction kettle in sequence, wherein the using amount of a carbon nano tube modified graphene oxide catalyst is 1-3% of the mass of raw material ethylene carbonate, the molar ratio of the raw material ethylene carbonate to the methanol is 1:2-1:10, and adding CO2Replacing the air in the autoclave for 2 times and refilling with CO2Heating to 0.5-1Mpa under magnetic stirring, heating to 100-120 deg.C, and reacting at the temperature for 4-6 h. Cooling to room temperature, taking reaction liquid, centrifugally separating and analyzing.
The catalyst graphene oxide can be prepared in a laboratory according to the following method:
in an ice-water bath, 5g of crystalline flake graphite, 2.5g of sodium nitrate and 115mL of concentrated sulfuric acid are uniformly mixed, and 15g of KMnO is slowly added while stirring4Keeping the temperature below 2 ℃ for continuous reaction for 1h, transferring the mixture to 35 ℃ water bath for reaction for 30min, gradually adding 250mL of deionized water, raising the temperature to 98 ℃ and continuing the reaction for 1h, wherein the mixture is obviously observed to be changed from dark brown to bright yellow. Further diluting with water continuously, and adding 30% by weight of H2O2And (4) solution treatment. And (3) carrying out suction filtration on the solution, washing the solution to be neutral by using a 5% HCl solution, and putting a filter cake into an oven to be fully dried at the temperature of 80 ℃ to obtain the graphite oxide. And (3) putting 0.1g of graphite oxide into 50mL of deionized water, carrying out ultrasonic treatment for 1.5h (180W, 60Hz), then carrying out suction filtration, and putting the filter cake into a vacuum oven for drying for 6h at 40 ℃ (10Pa) to obtain the required graphene oxide.
By adopting the technical scheme, the method has the advantages that the remarkable effect is achieved, the carbon nanotube modified graphene oxide is used as the catalyst, the energy consumption and the cost are greatly saved in the synthesis process of the dimethyl carbonate, the reaction time is shortened, the reaction temperature is reduced, and the catalyst dosage is reduced. Compared with pure graphene oxide, the distance between graphene oxide layers modified by the carbon nano tubes is greatly increased, so that oxygen-containing functional groups on the surfaces of the graphene oxide are completely exposed in a reaction system, and the catalytic efficiency is greatly increased. The reason for this is that the carbon nanotubes enter into the graphene oxide sheets during the modification process.
Detailed Description
The invention will be further described in the following examples, but it is to be understood that these examples are for illustrative purposes only and are not to be construed as limiting the practice of the invention.
Firstly, preparing a carbon nanotube modified graphene oxide catalyst: adding graphene oxide and carbon nanotubes into deionized water, performing ultrasonic treatment at room temperature for 2h, wherein the mass concentration of the graphene oxide in the deionized water is 1%, and then filtering and drying, wherein the mass ratio of the graphene oxide to the carbon nanotubes is 1:1-4: 1. The obtained catalyst was used in the following specific examples.
Example 1
Sequentially adding methanol, ethylene carbonate and carbon nano tube modified graphene oxide into a high-pressure reaction kettle, wherein the molar ratio of ethylene carbonate to methanol is 1:10, the mass ratio of graphene oxide to carbon nano tube in a catalyst is 1:1, the dosage of the catalyst is 1% of the mass of ethylene carbonate serving as a raw material, and using CO2Replacing the air in the autoclave for 2 times and refilling with CO2Heating to 0.5Mpa under magnetic stirring, heating to 100 deg.C, and reacting at the temperature for 6 h. Cooling to room temperature, taking reaction liquid, centrifugally separating and analyzing. The conversion rate of the ethylene carbonate is 82 percent, and the selectivity of the dimethyl carbonate is 99 percent.
Example 2
Sequentially adding methanol, ethylene carbonate and carbon nano tube modified graphene oxide into a high-pressure reaction kettle, wherein the molar ratio of ethylene carbonate to methanol is 1:10, the mass ratio of graphene oxide to carbon nano tube in a catalyst is 4:1, the dosage of the catalyst is 3% of the mass of ethylene carbonate serving as a raw material, and using CO2Replacing the air in the autoclave for 2 times and refilling with CO2Heating to 1Mpa under magnetic stirring, heating to 100 deg.C, and reacting at this temperature for 4 h. Cooling to room temperature, taking reaction liquid, centrifugally separating and analyzing. The conversion rate of ethylene carbonate is 85 percent, and the selectivity of dimethyl carbonate is 99 percent.
Example 3
Sequentially adding methanol, ethylene carbonate and carbon nano tube modified graphene oxide into a high-pressure reaction kettle, wherein the molar ratio of the ethylene carbonate to the methanol is 1:2, the mass ratio of the graphene oxide to the carbon nano tube in the catalyst is 2:1, the dosage of the catalyst is 2% of the mass of the raw material ethylene carbonate, and using CO2Replacing the air in the autoclave for 2 times and refilling with CO2Heating to 1Mpa under magnetic stirring, heating to 120 deg.C, and reacting at the temperature for 4 h. Cooling to room temperature, taking reaction liquid, centrifugally separating and analyzing. The conversion rate of the ethylene carbonate is 90 percent, and the selectivity of the dimethyl carbonate is 99 percent.
Example 4
Sequentially adding methanol, ethylene carbonate and carbon nano tube modified graphene oxide into a high-pressure reaction kettle, wherein the molar ratio of the ethylene carbonate to the methanol is 1:8, the mass ratio of the graphene oxide to the carbon nano tube in the catalyst is 2:1, the dosage of the catalyst is 2% of the mass of the raw material ethylene carbonate, and using CO2Replacing the air in the autoclave for 2 times and refilling with CO2Heating to 1Mpa under magnetic stirring, heating to 120 deg.C, and reacting at the temperature for 6 h. Cooling to room temperature, taking reaction liquid, centrifugally separating and analyzing. The conversion rate of the ethylene carbonate is 94 percent, and the selectivity of the dimethyl carbonate is 99 percent.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (2)
1. An application of a carbon nanotube modified graphene oxide catalyst in synthesizing dimethyl carbonate is characterized in that the application method of the catalyst is as follows:
ethylene carbonate and methanol are used as raw materials, wherein the molar ratio of the ethylene carbonate to the methanol is 1:2-1:10, carbon nanotube modified graphene oxide is used as a catalyst, the amount of the catalyst is 1-3% of the mass of the ethylene carbonate, the reaction is carried out in a high-pressure kettle, wherein the reaction temperature is 100-120 ℃, and the reaction atmosphere is CO-2The initial pressure is 0.5-1Mpa, and the reaction time is 4-6 hours.
2. The application of the carbon nanotube modified graphene oxide catalyst in the synthesis of dimethyl carbonate according to claim 1, wherein the carbon nanotube modified graphene oxide catalyst is prepared by the following method: adding graphene oxide and carbon nanotubes into deionized water, performing ultrasonic treatment at room temperature for 2h, and then filtering and drying, wherein the mass ratio of the graphene oxide to the carbon nanotubes is 1:1-4: 1.
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| CN108579789B (en) * | 2018-05-07 | 2021-06-01 | 常州大学 | Application of carbon nitride/graphene oxide composite material |
| CN109438409A (en) * | 2018-12-05 | 2019-03-08 | 常州大学 | A kind of method of synthesizing annular carbonate |
| CN109608337B (en) * | 2019-01-21 | 2020-04-17 | 山西大学 | Device and method for reinforcing alcoholysis process of ethylene carbonate |
| CN110304996B (en) * | 2019-06-28 | 2022-02-11 | 浙江锦润生物科技有限公司 | Method for removing alkali catalyst |
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| ATE440815T1 (en) * | 2005-10-10 | 2009-09-15 | Council Scient Ind Res | METHOD FOR PRODUCING DIALKYLCARBONATES |
| EP3099662B1 (en) * | 2014-01-30 | 2018-08-29 | Indian Oil Corporation Limited | Single-pot synthesis of dialkyl carbonates using catalyst from natural resource |
| CN104072377B (en) * | 2014-06-24 | 2016-04-06 | 常州大学 | A kind of method of cyclic carbonate and alcohol transesterification reaction synthetic linear carbonic ether |
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