CN100531904C - Catalyst used for catalytic synthesis for dimethyl carbonate directly from methanol and carbon dioxide, and preparation and using method thereof - Google Patents
Catalyst used for catalytic synthesis for dimethyl carbonate directly from methanol and carbon dioxide, and preparation and using method thereof Download PDFInfo
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- CN100531904C CN100531904C CNB2007100310065A CN200710031006A CN100531904C CN 100531904 C CN100531904 C CN 100531904C CN B2007100310065 A CNB2007100310065 A CN B2007100310065A CN 200710031006 A CN200710031006 A CN 200710031006A CN 100531904 C CN100531904 C CN 100531904C
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 18
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract 4
- 238000000034 method Methods 0.000 title abstract description 26
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 229910002804 graphite Inorganic materials 0.000 claims description 34
- 239000010439 graphite Substances 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002071 nanotube Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000012266 salt solution Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000969 carrier Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- -1 alkaline-earth metal alkoxy compound Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical class O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 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
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000003747 fuel oil additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002608 ionic liquid Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a direct catalytic synthesis catalyst to prepare dimethyl carbonate from methanol and carbon dioxide and the preparation and application methods of the catalyst. The catalyst of the invention consists of transitional metal soluble salt, promoter and carrier, with the weight ration from 0.01to 0.5: 0.01to 0.1:1. The preparation method is that: (1) the carrier is impregnated into the transition metal soluble salt solution; (2) the promoter is added into the solution, which is stirred in room temperature, ultrasonically dispersed and stored stationarily in room temperature; (3) the solution is dried, sintered, reduced and activated to produce catalyst. The application method is that: the catalyst is put in high pressure reactor or micro reaction device with the temperature of the catalyst bed controlled between 90 degrees centigrade to 140 degrees centigrade and the reaction pressure between 0.6 to 3.0MPa. The catalyst is applicable in direct catalytic synthesis to prepare dimethyl carbonate from methanol and carbon dioxide. The raw material sources are rich, the cost is low, the preparation method is simple and the operation is easy. The catalyst is easily separated from the products, the reaction conditions are mild and the catalyst can be used repeatedly. The catalyst has high activity and selectivity.
Description
Technical field
The present invention relates to a kind of catalyst that is used for Synthesis of dimethyl carbonate, preparation method and using method.
Background technology
Dimethyl carbonate (DMC) is a kind of important organic synthesis intermediate, be described as " new template " of organic synthesis, its can replace severe toxicity or carcinogenic materials such as phosgene, methylchloroformate, dimethyl suflfate and methyl chloride as carbonylation, methylate and methoxylation reagent, can be used for the initiation material of eco-friendly intermediate and organic synthesis.In recent years, DMC obtains application more and more widely in fields such as producing high performance resin, solvent, dyestuff intermediate, medicated premix, food preservative, fuel oil additive and is subject to people's attention day by day.At present, there is the patent of producing and using about DMC in a large number to deliver both at home and abroad, and the suitability for industrialized production of existing certain scale.The synthetic method that DMC is traditional mainly contains three major types: phosgenation, oxidative carbonylation of methanol method and ester-interchange method.A, phosgenation are traditional DMC synthetic methods, and this route uses phosgene to be raw material, produces the hydrogen chloride gas of severe corrosion equipment simultaneously, and the serious environmental pollution problem is eliminated gradually because the phosgene severe toxicity causes extremely; B, oxidative carbonylation of methanol method are primary raw material with the carbon monoxide, need additional expensive gas maker, and carbon monoxide has potential explosion hazard simultaneously; C, ester-interchange method earlier carry out cycloaddition by carbon dioxide and active epoxide, prepare target product by the ester exchange with methyl alcohol again, while by-product polyalcohol.This route steps is loaded down with trivial details, and course of reaction is restive, and separation of by-products is handled trouble.Present DMC is synthetic to adopt oxidative carbonylation of methanol method and ester-interchange method usually, but cost is higher, thereby has limited the extensive use of DMC.
In recent years, utilize cheap, nontoxic carbon dioxide to have bigger research, development and application potentiality for raw material and with the synthetic DMC of the direct catalysis of methyl alcohol.Not only be significant aspect synthetic chemistry, carbon resource utilization and the environmental protection by carbon dioxide and the synthetic DMC of the direct catalysis of methyl alcohol, and production process is simplified, production cost significantly reduces, and is the new way that development DMC produces.But because synthetic being reflected on the thermodynamics of DMC of carbon dioxide and the direct catalysis of methyl alcohol is disadvantageous, there is the water that makes catalysqt deactivation to generate simultaneously in the product, the restriction of above-mentioned two aspects causes in the building-up process selectivity of conversion of raw material and target product low, so the catalyst or the design coupled reaction that need design to have higher catalytic activity change means of chemical reaction, therefore explore different reaction paths, process conditions, in the hope of the carrying out and the raising product yield of driving a reaction, become a difficult problem and the focus of subject study.At present, carbon dioxide and the directly synthetic DMC of methyl alcohol have been done a large amount of research both at home and abroad.Employed catalyst system and catalyzing, comprise alkaline-earth metal alkoxy compound, alkali, acetate, organic metal tin, titanium alkoxide compound, carried metal class, zirconium dioxide class, the ceria class, organic tin and ionic liquid class etc., but subject matter is that the selectivity of the conversion ratio of reactant and target product is lower, course of reaction is restive, therefore is difficult to realize suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst that can be used for methyl alcohol and the direct catalytic synthesizing dimethyl carbonate of carbon dioxide.
It is simple that another object of the present invention provides a kind of step, the method for the above-mentioned catalyst of preparation that cost is low.
Further purpose of the present invention provides the using method of above-mentioned catalyst.
Of the present invention being used for is made up of the catalyst of methyl alcohol and the direct catalytic synthesizing dimethyl carbonate of carbon dioxide soluble salt, auxiliary agent and the carrier three by transition metal; The soluble salt of transition metal is in metal oxide, with the weight ratio of auxiliary agent, carrier be 0.01～0.5:0.01～0.1:1.
In above-mentioned catalyst, described transition metal is meant copper or nickel.As copper nitrate or copper sulphate or copper chloride etc., nickel nitrate or nickelous sulfate or nickel chloride etc.
In above-mentioned catalyst, described auxiliary agent is the oxide that contains rhodium, yttrium, vanadium, molybdenum, zirconium, yttrium, cerium, soluble-salt or oxysalt.
In above-mentioned catalyst, described carrier is graphite oxide, expanded graphite, CNT or active carbon.
Described graphite oxide carrier is by natural graphite powder, natural flake graphite or expansible graphite preparation, step is as follows: with natural graphite powder, natural flake graphite or expansible graphite in the presence of the concentrated sulfuric acid, potassium permanganate and sodium nitrate, in reacting below 4 ℃ 10～20 minutes, 35～38 ℃ were reacted 10～100 minutes down, reacted 15～90 minutes down at 90～100 ℃ again, product fully washs with 5% hydrochloric acid and deionized water, drying is 12～36 hours in 60～90 ℃ of vacuum drying chambers, obtains the graphite oxide carrier.
Described carbon nanotube carrier is by single wall or multi-walled carbon nano-tubes preparation, comprise the steps: SWCN or many walls nanotube in the presence of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 1:5～5:1, in 80～120 ℃ of following back flow reaction 6～36 hours, product fully washs with deionized water, 60～90 ℃ of following vacuum drying dryings 12～36 hours, obtain carbon nanotube carrier.
Described expanded graphite carrier is prepared by expansible graphite, comprises the steps: expansible graphite to obtain the expanded graphite carrier 700～1000 ℃ of following expanding treatments 5～30 seconds.
Described active carbon comprises coal mass active carbon, the fiber-reactive charcoal of cocoanut active charcoal or other kind.Can directly use commercially available active carbon, also can carry out modification to it and handle according to instructions for use, as oxidation modification, reduction modification, soda acid modification or with metal ion-modified etc.With the dense HNO of active carbon
3Handled 8～36 hours down at 20～100 ℃, wash neutrality, in baking oven,, get the absorbent charcoal carrier of oxidation processes in 40～150 ℃ of oven dry down.
Above-mentioned Preparation of catalysts method, comprise the steps: carrier impregnation in the solution of the soluble salt that contains transition metal, add auxiliary agent again, stirring at room 0.5～24 hour, ultrasonic dispersion 0.5～24 hour, room temperature were left standstill 2～30 hours, through 40～120 ℃ of dryings, reduce to room temperature at 200～600 ℃ of following roasts after 1～8 hour, use 5%H again
2/ 95%N
2Gaseous mixture obtained catalyst in 1～8 hour 300～800 ℃ of following reduction activations.
The using method of above-mentioned catalyst, comprise the steps for: catalyst is placed reaction under high pressure axe or micro-reaction device, the temperature of control beds is 90～140 ℃, reaction pressure is 0.6～3.0MPa, and product can directly enter gas-chromatography or detect its content with gauge line taking-up in good time and with gas chromatography-mass spectrography.
Compared with prior art, the present invention has following beneficial effect:
(1) catalyst of the present invention can be used for methyl alcohol and the direct catalytic synthesizing dimethyl carbonate of carbon dioxide, and synthetic raw material sources are abundant, and are with low cost.
(2) method for preparing catalyst of the present invention is simple, and is easy to operate.
(3) catalyst of the present invention separates easily with the product dimethyl carbonate, the reaction condition gentleness, and catalyst can be reused;
(4) catalyst activity height of the present invention, and selectivity is also high.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1
Accurately take by weighing the 10g native graphite, under agitation slowly join in ice-water bath is cooled to the 230ml concentrated sulfuric acid (98%) below 4 ℃, slowly add 5g sodium nitrate and 28g potassium permanganate again, stirring reaction 10 minutes.Remove ice bath, reaction system forwarded in 36 ℃ the hot bath to stirring reaction after 30 minutes, 95 ℃ of following stirring reactions 1 hour in oil bath again, product fully washs with 5% hydrochloric acid and deionized water, drying is 24 hours in 90 ℃ of vacuum drying chambers, obtains the graphite oxide carrier;
Accurately take by weighing 0.822gCu (NO
3)
23H
2O and 0.494gNi (NO
3)
26H
2O is dissolved in the 30ml absolute ethyl alcohol, with 2g graphite oxide carrier impregnation in above-mentioned metal salt solution, stirring at room 2 hours, ultrasonic dispersion 1 hour is after room temperature leaves standstill 12 hours, through 40 ℃ of dryings 2 hours, drying is 4 hours under 60 ℃, descended dry 12 hours at 90 ℃ again, reduce to room temperature after 3 hours, use 5%H again through 350 ℃ of following roasts
2/ 95%N
2Gaseous mixture obtained catalyst in 1.5 hours 600 ℃ of following reduction activations.
Take by weighing the above-mentioned catalyst of 1g, add on the miniature catalytic reaction experimental rig of MRS-901 and carry out the reactivity worth evaluation.By automatic control and the measurement that computer realization is formed temperature, pressure and reactant, the timing automatic sampling of product.Catalytic reaction condition is: 100 ℃ of temperature, and pressure 1.2MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1) adopts 102G-D type gas chromatograph assay products to form, and analysis result the results are shown in Table 1 by the coupling Computer Processing.
Embodiment 2
The preparing carriers method is with embodiment 1, and 2g graphite oxide carrier impregnation is to 0.4116gCu (NO
3)
23H
2O and 0.2476gNi (NO
3)
26H
2In the metal salt solution of O, all the other preparations and test condition the results are shown in Table 1 with embodiment 1.
Embodiment 3
The Preparation of Catalyst condition is with embodiment 1, and catalytic reaction condition is; 120 ℃ of temperature, pressure 1.2MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1), all the other test conditions the results are shown in Table 1 with embodiment 1.
Embodiment 4
The Preparation of Catalyst condition is with embodiment 1, and catalytic reaction condition is; 100 ℃ of temperature, pressure 1.4MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1), all the other test conditions the results are shown in Table 1 with embodiment 1.
Embodiment 5
The preparing carriers method is with embodiment 1, and 2g graphite oxide carrier impregnation is to 0.822gCu (NO
3)
23H
2O and 0.494gNi (NO
3)
26H
2In the metal salt solution of O, add 0.06gV again
2O
5, catalytic reaction condition is; 120 ℃ of temperature, pressure 1.3MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1), all the other test conditions the results are shown in Table 1 with embodiment 1.
Embodiment 6
Add the 30ml concentrated sulfuric acid and 30ml red fuming nitric acid (RFNA) in many walls of 5g nanotube, in 90 ℃ of following back flow reaction 24 hours, product fully washed with deionized water, dry 24 hours of 80 ℃ of following vacuum drying, obtains carbon nanotube carrier.
Accurately take by weighing 0.822gCu (NO
3)
23H
2O and 0.494gNi (NO
3)
26H
2O is dissolved in the 30ml absolute ethyl alcohol, many walls of 2g nano-tube support is impregnated in the above-mentioned metal salt solution, stirring at room 1 hour, ultrasonic dispersion is after 2 hours, after room temperature leaves standstill 12 hours, through 40 ℃ of dryings 2 hours, drying is 6 hours under 60 ℃, descended dry 12 hours at 90 ℃ again, reduce to room temperature after 3 hours, use 5%H again through 350 ℃ of following roasts
2/ 95%N
2Gaseous mixture obtained catalyst in 2 hours 600 ℃ of following reduction activations.The catalytic performance test of catalyst and the analytical method of product the results are shown in Table 1 with embodiment 1.
Embodiment 7
The preparing carriers method is with embodiment 6, and many walls of 2g nano-tube support is impregnated into 1.234gCu (NO
3)
23H
2O and 0.742gNi (NO
3)
26H
2In the metal salt solution of O, all the other preparations and test condition the results are shown in Table 1 with embodiment 6.
Embodiment 8
The preparing carriers method is with embodiment 6, and many walls of 2g nano-tube support is impregnated into 0.4116gCu (NO
3)
23H
2O and 0.2476gNi (NO
3)
26H
2In the metal salt solution of O, add 0.06gV again
2O
5, all the other preparations and test condition the results are shown in Table 1 with embodiment 6.
Embodiment 9
Expansible graphite 900 ℃ of following expanding treatments 10 seconds, is obtained the expanded graphite carrier.
Accurately take by weighing 0.411gCu (NO
3)
23H
2O and 0.247gNi (NO
3)
26H
2O is dissolved in the 30ml absolute ethyl alcohol, with 1g expanded graphite carrier impregnation in above-mentioned metal salt solution, stirring at room 2 hours, ultrasonic dispersion is after 1 hour, after room temperature leaves standstill 12 hours, through 40 ℃ of dryings 2 hours, drying is 6 hours under 60 ℃, descended dry 8 hours at 90 ℃ again, reduce to room temperature after 3 hours, use 5%H again through 350 ℃ of following roasts
2/ 95%N
2Gaseous mixture obtained catalyst in 4 hours 600 ℃ of following reduction activations.
The catalytic performance test of catalyst and the analytical method of product the results are shown in Table 1 with embodiment 1.
Embodiment 10
The preparing carriers method accurately takes by weighing 0.617gCu (NO with embodiment 9
3)
23H
2O and 0.371g Ni (NO
3)
26H
2O is dissolved in the 30ml absolute ethyl alcohol, and in above-mentioned metal salt solution, all the other preparation conditions are with embodiment 9 with 1g expanded graphite carrier impregnation.The catalytic performance test of catalyst and the analytical method of product the results are shown in Table 1 with embodiment 1.
Embodiment 11
The preparing carriers method is with embodiment 9, and 1g expanded graphite carrier impregnation is to 0.617gCu (NO
3)
23H
2O and 0.371g Ni (NO
3)
26H
2In the salting liquid of O, add 0.03gV again
2O
5, all the other preparation conditions are with embodiment 9.The catalytic performance test of catalyst and the analytical method of product the results are shown in Table 1 with embodiment 1.
Embodiment 12
The preparing carriers method is with embodiment 9, and catalytic reaction condition is; 120 ℃ of temperature, pressure 1.4MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1), all the other test conditions the results are shown in Table 1 with embodiment 1.
Table 1
| Embodiment | Methanol conversion (%) | DMC yield (%) | DMC selectivity (%) |
| 1 | 10.14 | 9.15 | 90.2 |
| 2 | 5.26 | 4.63 | 88.1 |
| 3 | 3.13 | 2.58 | 82.4 |
| 4 | 10.22 | 9.33 | 91.3 |
| 5 | 6.46 | 5.64 | 87.3 |
| 6 | 3.44 | 2.98 | 86.8 |
| 7 | 1.17 | 1.45 | 89.6 |
| 8 | 4.27 | 3.64 | 85.3 |
| 9 | 2.50 | 2.14 | 85.7 |
| 10 | 2.63 | 2.20 | 83.8 |
| 11 | 4.26 | 3.73 | 87.6 |
| 12 | 3.31 | 2.93 | 88.5 |
Claims (5)
1. a catalyst that is used for by methyl alcohol and the direct catalytic synthesis of C acid of carbon dioxide Ketene dimethyl is characterized in that being made by soluble salt, auxiliary agent and the carrier three of transition metal; The soluble salt of transition metal is in metal oxide, with the weight ratio of auxiliary agent, carrier be 0.01～0.5:0.01～0.1:1;
Described auxiliary agent is V
2O
5
Described transition metal is meant copper and mickel;
Described carrier is graphite oxide, expanded graphite, CNT or active carbon;
The preparation method comprises the steps: carrier impregnation in the solution of the soluble salt that contains transition metal, add auxiliary agent again, stirring at room 0.5～24 hour, ultrasonic dispersion 0.5～24 hour, room temperature left standstill 2～30 hours, through 40～120 ℃ of dryings, reduce to room temperature 200～600 ℃ of following roastings after 1～8 hour, use 5%H again
2/ 95%N
2Gaseous mixture obtained catalyst in 1～8 hour 300～800 ℃ of following reduction activations.
2. catalyst as claimed in claim 1, it is characterized in that described graphite oxide carrier is by natural graphite powder, natural flake graphite or expansible graphite preparation, step is as follows: with natural graphite powder, natural flake graphite or expansible graphite are at the concentrated sulfuric acid, potassium permanganate and sodium nitrate exist down, in reacting below 4 ℃ 10～20 minutes, 35～38 ℃ were reacted 10～100 minutes down, reacted 15～90 minutes down at 90～100 ℃ again, product fully washs with 5% hydrochloric acid and deionized water, drying is 12～36 hours in 60～90 ℃ of vacuum drying chambers, obtains the graphite oxide carrier.
3. catalyst as claimed in claim 1, it is characterized in that described carbon nanotube carrier is by single wall or multi-walled carbon nano-tubes preparation, comprise the steps: SWCN or many walls nanotube in the presence of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 1:5～5:1, in 80～120 ℃ of following back flow reaction 6～36 hours, product fully washs with deionized water, 60～90 ℃ of following vacuum drying 12～36 hours, obtains carbon nanotube carrier.
4. catalyst as claimed in claim 1 is characterized in that described expanded graphite carrier is prepared by expansible graphite, comprises the steps: expansible graphite to obtain the expanded graphite carrier 700～1000 ℃ of following expanding treatments 5～30 seconds.
5. catalyst as claimed in claim 1 is characterized in that described active carbon is a coal mass active carbon, the fiber-reactive charcoal of cocoanut active charcoal or other kind.
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| CN101632932B (en) * | 2009-08-28 | 2012-12-19 | 中山大学 | Dimethyl carbonate supported catalyst directly synthesized by methanol and carbon dioxide |
| CN101947425B (en) * | 2010-08-24 | 2013-05-08 | 中山大学 | Method for directly synthesizing dimethyl carbonate from methanol and carbon dioxide and special electrical assisted catalytic reactor |
| CN102659601B (en) * | 2012-06-05 | 2014-06-11 | 东北石油大学 | Synthesis method of dimethyl carbonate, catalyst and preparation method |
| CN102872879B (en) * | 2012-09-26 | 2014-11-19 | 太原理工大学 | Chlorine-free bimetallic catalyst for gas phase synthesis of dimethyl carbonate and preparation and application |
| CN103007940B (en) * | 2012-12-21 | 2014-12-03 | 云南大学 | Preparation method of catalyst in microwave-assisted catalytic oxidation treating process for imidacloprid pesticide waste water |
| CN103521266B (en) * | 2013-08-30 | 2015-05-06 | 重庆大学 | Composite catalyst for synthesizing dimethyl carbonate and preparation method of dimethyl carbonate |
| CN107652182A (en) * | 2017-09-18 | 2018-02-02 | 西北大学 | A kind of method using rare earth oxide as catalyst preparation dimethyl carbonate |
| TWI654178B (en) | 2017-12-28 | 2019-03-21 | 財團法人工業技術研究院 | Method for preparing dialkyl carbonate |
| CN109926056A (en) * | 2019-01-25 | 2019-06-25 | 浙江师范大学 | It is a kind of using carbon nanotube as the catalyst of carrier, preparation method and application |
| CN110479287A (en) * | 2019-09-12 | 2019-11-22 | 西南石油大学 | A kind of integral catalyzer for Synthesis of dimethyl carbonate and preparation method thereof, application method |
| CN112642481A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for preparing dialkyl carbonate from dialkyl oxalate, preparation method thereof and method for preparing dialkyl carbonate |
| TWI722719B (en) | 2019-12-16 | 2021-03-21 | 財團法人工業技術研究院 | Catalyst and precursor thereof and method of forming dialkyl carbonate |
| CN112275317B (en) * | 2020-11-04 | 2023-05-26 | 淮阴工学院 | Preparation of high-dispersity high-stability metal-loaded molecular sieve catalyst applied to carbon dioxide conversion |
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| CN85103556A (en) * | 1985-04-29 | 1986-10-29 | 化学工业部西南化工研究院 | Low steam carbon ratio hydrocarbon gas conversion catalyst and manufacturing thereof and purposes |
| CN1041968A (en) * | 1988-10-19 | 1990-05-09 | 中国科学院大连化学物理研究所 | Water at atmospheric pressure gas methanation active non-uniform type catalyzer and manufacture method thereof |
| CN1569329A (en) * | 2003-07-15 | 2005-01-26 | 四川大学 | Novel catalyst for methanol cracking reaction to produce CO and H2 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN85103556A (en) * | 1985-04-29 | 1986-10-29 | 化学工业部西南化工研究院 | Low steam carbon ratio hydrocarbon gas conversion catalyst and manufacturing thereof and purposes |
| CN1041968A (en) * | 1988-10-19 | 1990-05-09 | 中国科学院大连化学物理研究所 | Water at atmospheric pressure gas methanation active non-uniform type catalyzer and manufacture method thereof |
| CN1569329A (en) * | 2003-07-15 | 2005-01-26 | 四川大学 | Novel catalyst for methanol cracking reaction to produce CO and H2 |
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