CN101613339B - Method for synthesizing ethylene carbonate and catalyst therefor - Google Patents
Method for synthesizing ethylene carbonate and catalyst therefor Download PDFInfo
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- oxyethane
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- 238000000034 method Methods 0.000 title claims abstract description 48
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000011089 carbon dioxide Nutrition 0.000 claims description 25
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 230000000536 complexating effect Effects 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 3
- 239000001569 carbon dioxide Substances 0.000 abstract 3
- 150000004696 coordination complex Chemical class 0.000 abstract 2
- 230000009977 dual effect Effects 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 229910052728 basic metal Inorganic materials 0.000 description 5
- 150000003818 basic metals Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing ethylene carbonate, comprising ethylene oxide and carbon dioxide are obtained by the reaction under the condition of catalysis of dual metal complex immobilized type granule catalyst; the reaction process and condition include: the ethylene oxide and the dual metal complex catalyst are added into a high pressure reaction kettle, the carbon dioxide is filled into the reaction kettle, the temperature is raised to 120-190 DEG C which is maintained for 2-3h, and then the temperature is reduced to 60 DEG C; after that, the pressure is reduced to be ordinary pressure, and the ethylene carbonate can be obtained after filtration. The ethylene carbonate prepared by the method has the advantages of little dosage of the catalyst, cycle use, low reaction temperature and pressure, high product yield, raw material conversion per pass, selectivity and space time yield and the like; furthermore, the method is also applicable to preparing the ethylene carbonate by using the ethylene oxide and the carbon dioxide.
Description
Technical field
The present invention relates to a kind of method of synthesizing ethylene carbonate, particularly is the method and the catalyzer of main raw material reaction synthesizing ethylene carbonate with oxyethane and carbonic acid gas.
Background technology
NSC 11801 (being called for short EG), it is in the middle of a kind of fine chemistry industry of excellent property, is potential basic material in the 21 century organic chemical industry industry.NSC 11801 can be used as the solvent of weaving, printing and dyeing, Polymer Synthesizing and electrochemistry aspect.Particularly in recent years, EG is applied to the production of lithium cell and methylcarbonate; Aliphatic polycarbonate and comprise the multipolymer of carbonate monomer begins to be used as biodegradable material, and the research in this field is more paid attention to.
The synthetic report of NSC 11801 starts from the beginning of the eighties of last century, and industrialized compound method the earliest is the phosgene synthesis method, because phosgene has severe toxicity and environment is produced serious pollution, this method is in developed country's use that has been under an embargo at present.Develop ester-interchange method subsequently, the method that promptly prepares by the transesterification reaction of diethyl carbonate and terepthaloyl moietie, this method is little with respect to phosgenation toxicity, and operability will be got well.Though the report about this reaction is a lot, the catalytic effect of the catalyzer of being reported is not very good, and the reaction product yield is not high, and selectivity is relatively poor.
Studied the compound method that mainly concentrates on carbonic acid gas and oxyethane direct reaction generation NSC 11801 since mid-term from eighties of last century; Carbonic acid gas and oxyethane synthesizing ethylene carbonate have at first been realized suitability for industrialized production in the Germany, and early stage compound method all adopts the homogeneous phase method.[Mitsui Petrochemical Industries Ltd.Preparationof cyclic carbonates [P] .US 4880942 such as Yoshihisa K; 1989-11-14.] be catalyzer with earth alkali metal or basic metal; Methylcarbonate is as diethyl carbonate and terepthaloyl moietie or 1, and the surrogate of 2-Ucar 35 is used to prepare NSC 11801 or propylene carbonate.When using sodium hydroxide as catalyzer, reaction 12h under 144 ℃, normal pressure, the yield of NSC 11801 is 88%.The patent of Bayer AG [Wagner, et al.US 5,350,862.1996-04-16] has been described a kind of method that adopts basic metal bromine, basic metal iodine, tetramethyl-amine bromide, tetramethyl-iodate amine catalyst synthesizing ethylene carbonate.Patent [the Birnbach of BASF AG; Et al.US6; 265; 592.2001-07-4] a kind of method through corresponding epoxide and the liquid phase reaction continuous production NSC 11801 of carbonic acid gas in the presence of tetraethyl-amine bromide catalyzer is disclosed, this method is reacted in two steps, and the final product yield can reach 99.5%.Tang Zhanzhong, gold woods be at " study on the synthesis of NSC 11801 " " petrochemical complex " .1996, and 25 (6): be catalyzer then in 409～413 with the KI/PEG complex compound, and the influence to reaction of research different molecular weight PEG; Conclusion is the best results of PEG400 (ECC-1); Close with crown ether, cost but reduces greatly, confirms optimum process condition simultaneously: 120～140 ℃ of temperature of reaction; Reaction pressure 2.5～3.0MPa, ECC-1: EO=(0.006～0.009): 1.China Dong Lian of Taiwan Province chemical company is catalyzer (concentration is 0.5%～2%) with tetraethyl-amine bromide or potassiumiodide, makes solvent with EC, makes EO and CO
2Reaction generates EC under 100～200 ℃, 1～2MPa.Though the homogeneous catalysis compound method has higher catalytic efficiency and raw material availability; But the homogeneous phase method exists that resultant is difficult to be separated, and catalyst levels is big, and can not recycling; The wasting of resources and more serious to environmental stress is simultaneously to the also more high shortcoming of the requirement of catalyzer.
In recent years, investigators focused on again on the heterogeneous method, and the relative homogeneous phase method of heterogeneous method has resultant and catalyzer easily separated, and catalyzer is prone to regeneration and advantage such as can repeatedly recycles.MOBIL OILS [Buchanan, et al.US6,258,962.2001-07-21] has developed a kind of method of in the presence of the porous solid carrier catalyzer of alkaline including earth metal, reacting synthesizing ethylene carbonate through alkylene oxide and carbonic acid gas.Wang Changfeng; Han Sen; Xia Yongde etc. " superpolymer immobilized nitrogenous with contain the preparation and the catalytic activity of phosphine part complex catalyst " " IX and absorption " .1998; 14 (2): 104～109, develop a kind of be used for carbonic acid gas and oxyethane at nitrogenous, as to contain phosphine part functional polymer solid-carried catalyst (through chemical bond and MC1
2Link) there is the method for synthesizing ethylene carbonate down, the carrier of this functional polymer is chloromethylated polystyrene-divinylbenzene resin, and the oxyethane transformation efficiency is 93%, and the selectivity of EC is 100%.[the Sun Yuhan of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences; Wei Wei; The Li Qi violent wind; Zhao Ning. the method .CN 02155480.3 of a kind of synthesizing acrylic ester or NSC 11801; 2002-12-16] the solid catalyst method of a kind of novel synthesizing ethylene carbonate of report, this method belongs on the research basis of oxyethane liquid-phase catalyst method for many years through this, develops the oxyethane solid catalyst method that technology more simply adopts the solid catalyst synthesizing ethylene carbonate; This technology also has characteristics such as technical process is short, product is easily separated, be prone to purifying, energy consumption is low except that having the advantage of reaction conditions than homogeneous phase method gentle (temperature of reaction is lower than 180 ℃, reaction pressure and is lower than 8.0MPa).Doskocil E J [Doskocil EJ. [J] .Microporous and Mesoporous Materials, 2004,76 (1-3): 177-183.] is with molecular sieve carried various basic metal of ETS-10 and earth alkali metal.As of the addition reaction of catalyst research carbonic acid gas to propylene oxide.The result shows that the activity of basic metal supported catalyst is higher than the activity of earth alkali metal supported catalyst, and under the same reaction conditions, the ETS-10 catalyzer of caesium load shows the highest catalytic activity.
But the good catalytic effect and the yield of product not only to be arranged as good catalytic production technology; Also to make process economics, practicality, be easy to change into industrial production; Above-mentioned process method only satisfies wherein a kind of or two kinds of conditions; Thereby Many researchers also finds the method for better synthesizing ethylene carbonate in exploration.
Summary of the invention
The object of the present invention is to provide a kind of method of advantages of simple, so that prepare NSC 11801 with cheap cost.With carbonic acid gas and oxyethane is raw material, bimetal complexing solid-carrying type beaded catalyst, thus reach the method for mild condition, high catalytic efficiency (, highly selective, synthesizing ethylene carbonate such as with low cost.
The technical scheme that the inventive method is concrete is following:
The method of synthesizing ethylene carbonate is oxyethane and carbonic acid gas to be reacted obtain under the catalytic situation of bimetal complexing solid-carrying type beaded catalyst; Described reaction conditions is: oxyethane and bimetal complexing solid-carrying type beaded catalyst are added in the reaction autoclave, and wherein the add-on of catalyzer is 0.1～0.5% of an oxyethane consumption, and in reaction kettle, charging into carbonic acid gas to pressure then is 2MPa～5MPa; Wherein the mol ratio of oxyethane and carbonic acid gas is 1: 1.05～1.1; And be warming up to 120 ℃～190 ℃, and keep above temperature, pressure after 2 to 3 hours, be cooled to 60 ℃; Be depressurized to normal pressure, filter and make NSC 11801.Experiment has obtained effect preferably, and the conversion of oxyethane reaches 99% in detection reaction, and the selectivity of NSC 11801 reaches 99%.Filter after the NSC 11801, catalyzer can be recycled.
The bimetal complexing solid-carrying type beaded catalyst of the above synthesizing ethylene carbonate method specifically can be expressed as M
1 a[M
2(I)
b]/L, wherein: M
1For: K, Ca; M
2For: Cu, Pd; L is a carrier: comprise SiO
2Or activated carbon; A=1,2, b=2,4: be coefficient.
Described bimetal complexing solid-carrying type beaded catalyst M
1 a[M
2(I)
bThe concrete preparation technique scheme of]/L is following:
At room temperature, take by weighing a certain amount of L (carrier), take by weighing a certain amount of M in 100 ℃ of drying 3～4h
2Muriate be made into the solution of 0.5～1M with zero(ppm) water, take by weighing a certain amount of M
1Salt compounded of iodine be made into the solution of 0.5～1M with zero(ppm) water.Under constant temperature, measure a certain amount of above-mentioned institute and join M
2Chloride soln place reactor drum, under induction stirring, slowly drip the above-mentioned M for preparing then
1Iodized salt solution, dripping quantity is M
1With M
2Mol ratio 2: 1, for deposition to be generated stable after, cross and filter filter cake, again with deionized water wash filter cake 2～3 times.The gained filter cake is put into reactor drum, under constantly stirring, slowly be added dropwise to M
1Iodized salt solution, to just dissolving fully of deposition, stop to drip.Press M
2: the ratio of L=0.0125mol: 1g adds the L carrier again, and it is mixed, and is evaporated to reaction mixture dried at normal temperatures.Then in baking oven in 110 ℃ of following vacuum-dryings to constant weight, the solid compressing tablet that obtains is shaped, and grinds then, final sizing becomes 100 orders to make catalyzer.
The present invention compared with prior art, its substantive distinguishing features and obvious improvement are:
What 1) adopted is bimetal complex solid-carrying type particulate catalytic technology, has better practicability through this process method of experiment confirm, temperature required lower with pressure in the reaction process;
2) reaction process is simple, controls easily and operates, and is easy to realize the industriallization amplification;
3) the reaction catalyst system therefor is cheap and easy to get, and consumption is merely 0.1～0.5% of oxyethane consumption, and simultaneously catalytic performance is stable, good reproducibility, and catalyst levels is little and can be recycled.
4) reaction times weak point, feed stock conversion approaches theoretical value, and selectivity of product is high, and the by product of reaction is few, so the economy of method is very obvious.
5) this technology also is applicable to propylene oxide and carbonic acid gas and makes propylene carbonate.
Embodiment
In order to understand the present invention better, further set forth below in conjunction with embodiment, but these embodiment should not be construed as any restriction of the present invention.
Embodiment 1
Under constant temperature, measure 0.5mol/LCuCl
2Solution 50mL places reactor drum, under induction stirring, slowly drips 0.5mol/LKI solution 100mL then, after deposition to be generated is stable, crosses and filters filter cake, again with deionized water wash filter cake 3 times.The gained filter cake is put into reactor drum, under constantly stirring, slowly be added dropwise to KI solution,, stop to drip to just dissolving fully of deposition.Add 2g solid SiO again
2Carrier, it is mixed after, reaction mixture is evaporated at normal temperatures dried, the consisting of of gained catalyzer: KCuI
2/ SiO
2Then in baking oven in 110 ℃ of following vacuum-dryings to constant weight, the solid compressing tablet that obtains is shaped, and grinds then, final sizing becomes 100 orders to make catalyzer.Device is FYX-1 type autoclave, and catalyst levels is 1.0g, oxyethane 500.0g; Carbonic acid gas is feeding in 1: 1.1 by the mol ratio of oxyethane and carbonic acid gas; Obtain NSC 11801 after the reaction, filter after the NSC 11801, catalyzer can continue to recycle.Above-mentioned reaction conditions and gained result are following:
| Temperature ℃ | Pressure Mpa | Reaction times h | EO transformation efficiency % | EC yield % | EC selectivity % |
| 190 | 5.0 | 3 | 99.00 | 98 | 100 |
Embodiment 2: reaction process is with embodiment 1, and catalyzer is KCuI
2/ SiO
2Catalyst levels is 1.2g, oxyethane 500.0g, and carbonic acid gas is feeding in 1: 1.05 by the mol ratio of oxyethane and carbonic acid gas.Reaction conditions and gained result are following:
| Temperature ℃ | Pressure Mpa | Reaction times h | EO transformation efficiency % | EC yield % | EC selectivity % |
| 170 | 2.0 | 2 | 97.00 | 96 | 100 |
Embodiment 3: reaction process is with embodiment 1, and catalyzer is K
2PdI
4/ activated carbon.Catalyst levels is 1.0g, oxyethane 500.0g, and carbonic acid gas is feeding in 1: 1.1 by the mol ratio of oxyethane and carbonic acid gas.Reaction conditions and result are following:
| Temperature ℃ | Pressure Mpa | Reaction times h | EO transformation efficiency % | EC yield % | EC selectivity % |
| 150 | 3.5 | 3 | 80.00 | 86 | 91 |
Embodiment 4: reaction process is with embodiment 1, and catalyzer is K
2PdI
4/ activated carbon.Catalyst levels is 0.8g, oxyethane 300.0g, and carbonic acid gas is feeding in 1: 1.1 by the mol ratio of oxyethane and carbonic acid gas.Reaction conditions and result are following:
| Temperature ℃ | Pressure Mpa | Reaction times h | EO transformation efficiency % | EC yield % | EC selectivity % |
| 120 | 2.0 | ?2 | 65.00 | 74 | 82 |
Embodiment 5: reaction process is with embodiment 1, and catalyzer is CaPdI
4/ SiO
2Catalyst levels is 1.0g, oxyethane 200.0g, and carbonic acid gas is feeding in 1: 1.1 by the mol ratio of oxyethane and carbonic acid gas.Reaction conditions and result are following:
| Temperature ℃ | Pressure Mpa | Reaction times h | EO transformation efficiency % | EC yield % | EC selectivity % |
| 130 | 5.0 | 2.5 | 83.00 | 88 | 94 |
Claims (2)
1. the method for a synthesizing ethylene carbonate; It is characterized in that: be oxyethane and carbonic acid gas to be reacted obtain under the catalytic situation of bimetal complexing solid-carrying type beaded catalyst; Described reaction process and condition are: oxyethane and bimetal complexing solid-carrying type beaded catalyst are added in the reaction autoclave, and wherein the add-on of catalyzer is 0.1～0.5% of an oxyethane consumption, and in reaction kettle, feeding carbonic acid gas to pressure then is 2MPa～5MPa; Wherein the mol ratio of oxyethane and carbonic acid gas is 1: 1.05～1.1; And be warming up to 120 ℃～190 ℃, and keep above temperature, pressure after 2 to 3 hours, be cooled to 60 ℃; Be depressurized to normal pressure, filter and make NSC 11801;
Described bimetal complexing solid-carrying type beaded catalyst is M
1 a[M
2(I)
b]/L bimetal complexing solid-carrying type beaded catalyst, wherein:
M
1For: K, Ca;
M
2For: Cu, Pd;
L is a carrier: comprise SiO
2And activated carbon;
A=1,2, b=2,4: be coefficient.
2. the method for synthesizing ethylene carbonate according to claim 1, it is characterized in that: the preparation method of described bimetal complexing solid-carrying type beaded catalyst is: at room temperature, take by weighing a certain amount of carrier L in 100 ℃ of drying 3～4h, take by weighing a certain amount of M
2Muriate be made into the solution of 0.5～1M with zero(ppm) water, take by weighing a certain amount of M
1Salt compounded of iodine be made into the solution of 0.5～1M with zero(ppm) water, under constant temperature, measure a certain amount of above-mentioned institute and join M
2Chloride soln place reactor drum, under induction stirring, slowly drip the above-mentioned M for preparing then
1Iodized salt solution, dripping quantity is M
1With M
2Mol ratio 2: 1, for deposition to be generated stable after, cross and filter filter cake, with deionized water wash filter cake 2～3 times, the gained filter cake is put into reactor drum again, under constantly stirring, slowly be added dropwise to M
1Iodized salt solution, to just dissolving fully of deposition, stop to drip, press M
2: the ratio of L=0.0125mol: 1g adds the L carrier again, and it is mixed, and is evaporated to reaction mixture dried at normal temperatures; Then in baking oven in 110 ℃ of following vacuum-dryings to constant weight; The solid compressing tablet that obtains is shaped, and grinds then, and final sizing becomes 100 orders to make catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101142600A CN101613339B (en) | 2009-07-27 | 2009-07-27 | Method for synthesizing ethylene carbonate and catalyst therefor |
Applications Claiming Priority (1)
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| CN103896905B (en) * | 2012-12-27 | 2016-04-13 | 中国石油化工股份有限公司 | The method of ethylene (propylene) carbonate is prepared for epoxide and carbonic acid gas |
| CN103172608A (en) * | 2013-03-22 | 2013-06-26 | 中国科学院过程工程研究所 | Method for preparing cyclic carbonate through catalysis of amino acid composite catalyst |
| CN110003163A (en) * | 2019-04-30 | 2019-07-12 | 大连理工大学 | A kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate |
| CN114768884B (en) * | 2022-05-05 | 2023-06-30 | 四川鸿鹏新材料有限公司 | Immobilized catalyst for producing ethylene carbonate, preparation method and application |
| CN115385888A (en) * | 2022-10-31 | 2022-11-25 | 山东海科新源材料科技股份有限公司 | Production device and method for synthesizing ethylene carbonate |
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