CN102295632B - Method for preparing ethylene carbonate from ethylene oxide and carbon dioxide - Google Patents

Method for preparing ethylene carbonate from ethylene oxide and carbon dioxide Download PDF

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CN102295632B
CN102295632B CN2010102080731A CN201010208073A CN102295632B CN 102295632 B CN102295632 B CN 102295632B CN 2010102080731 A CN2010102080731 A CN 2010102080731A CN 201010208073 A CN201010208073 A CN 201010208073A CN 102295632 B CN102295632 B CN 102295632B
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oxyethane
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carbonic acid
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陈梁锋
何文军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method for preparing ethylene carbonate from ethylene oxide and carbon dioxide, which mainly solves the problems of low catalyst activity and high probability of loss of active ingredients existing in the prior art. In the method, the ethylene oxide and the carbon dioxide are utilized as raw materials; the reaction raw materials are contacted with a catalyst to generate the ethylene carbonate under the conditions of reaction temperature of 50-200 DEG C, reaction pressure of 0.1-10.0MPa and mass ratio of the catalyst to the ethylene carbonate of 0.001-1:1; and in the catalyst, SiO2 microspheres with average diameter of 15-500nm are used as a nuclear phase, and metal salt MYn complexed by polyethyleneimine is used as a shell phase, wherein M is Ni, Zn, Cu, Fe or Co; Y is Cl, Br or I; and n is 2 or 3. The periphery of the nuclear-phase nano SiO2 spheres is wrapped by a metal salt shell layer complexed by the polyethyleneimine; the thickness of the shell layer is 0.5-8nm; and the weight ratio of the nuclear phase to the shell phase is 45/55-99.5/0.5. Due to the technical scheme, the problem is solved better; and the method can be used for industrial production of the ethylene carbonate from the ethylene oxide and the carbon dioxide.

Description

Be used for the method that oxyethane and carbonic acid gas prepare NSC 11801
Technical field
The present invention relates to a kind of method for preparing NSC 11801 for oxyethane and carbonic acid gas.
Background technology
NSC 11801 is a kind of solvent and fine-chemical intermediate of excellent property, is the potential basic material of organic chemical industry.Simultaneously, CO 2A kind of greenhouse gases, effective fixing one of challenging problem of tool in this century that become how.And by oxyethane and CO 2The reaction synthesizing ethylene carbonate is exactly a kind of good fixing means wherein.Along with recently take NSC 11801 as the raw material co-producing dimethyl carbonate and glycol reaction day by day receive publicity, by NSC 11801 fixation of C O 2Approach also be subject to increasing attention.
The method majority of the production NSC 11801 of having reported at present is the binary homogeneous catalyst that uses Lewis acid metal compound and Lewis alkali to form, use therein Lewis acid metal compound comprises alkali (soil) metal halide, transition metal salt, transition metal or main group metal title complex, employed Lewis alkali has organic bases (such as DMF, DMAP etc.), quaternary ammonium salt, quaternary alkylphosphonium salt, imidazole salts, crown ether etc.These catalyst system or activity, selectivity are not high, have perhaps used the very strong organic solvent of toxicity, and the homogeneous catalysis system shortcoming that exists catalyzer to be difficult to separate.And use at present more heterogeneous catalysis system to comprise that the metal oxide system is (such as CeO 2-ZrO 2, Green Chem.2004,6,206-214), the basic zeolite system (such as Cs/KX, J.Catal.2001,199,85-91) etc., these catalyst system activity are low, the needed reaction times is longer.Xia Chungu etc. are with ZnCl 2Immobilized on chitin carrier, although obtained higher catalytic activity, catalyzer has been applied mechanically after 5 times activity decreaseds about 8%.Infer that possible reason is that (Appl.Catal.A 2005,279,125-129) for the loss of catalyst activity component.Therefore, develop a kind of easily separated, active high, reaction conditions catalyst system gentle, that be difficult for inactivation and seem very important.
Summary of the invention
The problem that technical problem to be solved by this invention is that the catalyst activity that exists in the conventional art is low, active ingredient easily runs off provides a kind of new method that oxyethane and carbonic acid gas prepare NSC 11801 that is used for.The method has the catalyst activity height, is difficult for the characteristics of inactivation.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing NSC 11801 for oxyethane and carbonic acid gas, take oxyethane and carbonic acid gas as raw material, it is 50～200 ℃ in temperature of reaction, reaction pressure is 0.1～10.0MPa, the mass ratio of catalyzer and oxyethane is (0.001～1): under 1 the condition, reaction raw materials contacts the Formed vinyl acetate with catalyzer; Wherein said catalyzer is take the SiO of mean diameter as 15～500 nanometers 2Microballoon is nuclear phase, with the metal-salt MY of polymine complexing nBe the shell phase, wherein M is Ni, Zn, Cu, Fe or Co, and Y is Cl, Br or I, and n is 2 or 3; Nuclear phase SiO 2The periphery of microballoon is wrapped in the metal salt crust phase of polymine complexing, and the shell phase thickness is 0.5～8 nanometer, shell mutually in the weight ratio of polymine and metal-salt be 0.3～10, nuclear phase is 45/55～99.5/0.5 with weight ratio between the shell phase.
In the technique scheme, nuclear phase SiO 2The mean diameter preferable range of microballoon is 20～450 nanometers, and more preferably scope is 25～400 nanometers.The thickness preferable range of shell phase is 1～6 nanometer, and more preferably scope is 1～4 nanometer.The shell mutually molecular-weight average of middle polymine is preferable range 1000～20000, and more preferably scope is 1000～16000.Shell mutually in the weight ratio preferable range of polymine and metal-salt be 0.3～9, more preferably scope is 0.3～8.Nuclear phase and the shell weight ratio preferable range between mutually is 50/50～99.2/0.8, and more preferably scope is 55/45～99/1.The preferable range of reaction conditions is: temperature of reaction is 60～180 ℃, and reaction pressure is 0.5～8.0MPa, and the mass ratio of catalyzer and oxyethane is (0.002～0.8): 1.The preparation method of used catalyzer may further comprise the steps among the present invention:
A) ammoniacal liquor is added in the mixed solution of alkanol and deionized water, form solution A; Described alkanol is at least a in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the Pentyl alcohol; Wherein, the mol ratio of ammonia and alkanol is 0.01～2, and the mol ratio of deionized water and alkanol is 0.2～10;
B) under the condition that ultrasonic wave exists, in solution A, drip tetraalkyl orthosilicate, produce throw out nanometer SiO 2Microballoon; Described tetraalkyl orthosilicate is tetraethoxy or methyl silicate; Wherein, hyperacoustic power is 40～400W, and tetraalkyl orthosilicate and step a) mol ratio of middle alkanol are 0.01～0.1;
C) with nanometer SiO 2Microballoon with deionized water wash after, again be scattered in the deionized water with ultrasonic, obtain mixture B;
D) add the mixing solutions of polymine and Repone K in the mixture B, 30～60 ℃ lower stir 0.5～10 hour after, centrifugation obtains solid C; Wherein polymine and nanometer SiO 2The mass ratio of microballoon is 0.01～0.3, Repone K and nanometer SiO 2The mass ratio of microballoon is 0.02～0.5;
E) with solid C with washing with alcohol after, add metal-salt MY nChain triacontanol solution in, room temperature leaves standstill filtration after 0.5～5 hour, washing, drying, obtains described catalyzer; Wherein, metal-salt MY nWith nanometer SiO 2The mass ratio of microballoon is 0.05～0.63.
The present invention adopts hud typed catalyzer, and nuclear phase is the SiO of high dispersive 2Nano microsphere utilizes the part NH group effect of its surperficial part silicon hydroxyl and polymine (PEI) to coat one deck PEI film, then by all the other NH group chelated mineral salt MY of PEI n, PEI and MY nMixture form the shell phase because the chain of chain polymer PEI is soft, it is high to contain the N amount, so itself and SiO 2The silicon hydroxyl on Nano microsphere surface and the effect of metal-salt are multidigit points, but and the amount of the metal-salt of complexing larger, disperse also better, the catalyst with core-casing structure specific activity that so forms is higher, also more stable.Be 100 ℃ in temperature of reaction, reaction pressure is 2.0MPa, and the mass ratio of catalyzer and oxyethane is reaction 3 hours under 0.02: 1 the condition, the NSC 11801 yield can reach 99%, catalyzer is applied mechanically 5 times after filtering, and activity decreased has been obtained preferably technique effect less than 5%.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
18.0 milliliters of the strong aquas of 25 % by weight are added in the mixing solutions of 80.0 ml deionized water and 890.0 milliliters of ethanol (mol ratio of ammonia and ethanol is 0.016, and the mol ratio of deionized water and ethanol is 0.29).When the 40W ultrasonic wave exists, to mixed solution and dripping 41.6 gram tetraethoxys (TEOS, the mol ratio of TEOS and ethanol is 0.013).Drip rear continuation with the ultrasonication of equal-wattage after 3 hours centrifugation go out throw out.Behind deionized water wash, with resulting SiO 2Then Nano microsphere again ultra-sonic dispersion contains the aqueous solution (PEI and the SiO that polymine (PEI, molecular-weight average 1600) 3.3 restrains and KCl 5.1 restrains to wherein adding 200 milliliters in 200 ml deionized water 2The weight ratio of Nano microsphere is 0.29, KCl and SiO 2The weight ratio of Nano microsphere is 0.45).60 ℃ of stirring centrifugations after 4 hours, with the resulting solid of washing with alcohol, then its adding is contained ZnCl 25.9 (PEI and ZnCl in 100 milliliters of ethanolic solns of gram 2Weight ratio be 0.56, ZnCl 2With SiO 2The weight ratio of Nano microsphere is 0.52), room temperature leaves standstill after 4 hours and filters, and uses washing with alcohol, 130 ℃ of dried overnight, obtains catalyst A.
The structure of this catalyzer is found after transmission electron microscope (TEM) is observed, nuclear phase SiO 2The mean diameter of microballoon is 31 nanometers, and the shell phase thickness is 3.5 nanometers.Through comparing catalyst A and nanometer SiO 2The weight ratio that obtains nuclear phase and shell phase after the weight of microballoon is 57/43.
With the reaction of catalyst A for oxyethane and carbonic acid gas, condition is as follows: add 150.0 gram oxyethane and 3.0 gram catalyzer in 300 milliliters of autoclaves, be filled with 1.0MPa CO 2, be warming up to 100 ℃, be filled with again CO 2, keep reaction pressure at 2.0MPa, react and remove by filter catalyzer after 3 hours.Record oxyethane transformation efficiency (C EOBe 95.4% %), NSC 11801 selectivity (S ECBe 99.5% %).
[embodiment 2]
285.0 milliliters of the strong aquas of 25 % by weight are added in the mixing solutions of 349.1 ml deionized water and 81.0 ml methanol (mol ratio of ammonia and methyl alcohol is 1.9, and the mol ratio of deionized water and methyl alcohol is 9.7).When the 400W ultrasonic wave exists, to mixed solution and dripping 30.4 gram methyl silicates (TMOS, the mol ratio of TMOS and methyl alcohol is 0.1).Drip rear continuation with the ultrasonication of equal-wattage after 3 hours centrifugation go out throw out, behind deionized water wash, with resulting SiO 2Then Nano microsphere again ultra-sonic dispersion contains the aqueous solution (PEI and the SiO that polymine (PEI, molecular-weight average 16000) 0.13 restrains and KCl 0.25 restrains to wherein adding 200 milliliters in 200 ml deionized water 2The weight ratio of Nano microsphere is 0.011, KCl and SiO 2The weight ratio of Nano microsphere is 0.020).30 ℃ of stirring centrifugations after 0.5 hour, with the resulting solid of washing with alcohol, then its adding is contained ZnCl 20.98 (PEI and ZnCl in 100 milliliters of ethanolic solns of gram 2Weight ratio be 7.5, ZnCl 2With SiO 2The weight ratio of Nano microsphere is 0.083), room temperature leaves standstill after 0.6 hour and filters, and uses washing with alcohol, 70 ℃ of dried overnight, obtains catalyst B.
The structure of this catalyzer is found after transmission electron microscope (TEM) is observed, nuclear phase SiO 2The mean diameter of microballoon is 345 nanometers, and the shell phase thickness is 1.1 nanometers.Through comparing catalyst B and nanometer SiO 2The weight ratio that obtains nuclear phase and shell phase after the weight of microballoon is 91.5/8.5.
With the reaction of catalyst B for oxyethane and carbonic acid gas, condition is with [embodiment 1].Reaction result is as follows: the oxyethane transformation efficiency is 39.4%, and the NSC 11801 selectivity is 98.9%.
[embodiment 3～6]
Change the amount of employed strong aqua, the molecular-weight average of employed PEI is 6600, and all the other operation stepss are all with [embodiment 1], the nuclear phase of the nucleocapsid catalyst that obtains/shell phase weight ratio, PEI and ZnCl 2Weight ratio all consistent with [embodiment 1], with the nuclear phase SiO of nucleocapsid catalyst 2Catalytic activity under microballoon mean diameter and shell phase thickness and the same terms is listed in table 1.
Table 1
Figure BSA00000166817600041
[embodiment 7～10]
Change used ultrasonic power, all the other operation stepss are all with [embodiment 1].Nuclear phase shell phase weight ratio, PEI and the ZnCl of the nucleocapsid catalyst that obtains 2Weight ratio all consistent with [embodiment 1], the nuclear phase mean diameter of nucleocapsid catalyst and the catalytic activity under shell phase thickness and the same terms are listed in table 2.
Table 2
[embodiment 11～14]
Change used PEI and ZnCl 2Weight, all the other steps are with [embodiment 1].The character of the nucleocapsid catalyst that obtains and the catalytic activity under the same terms are listed in table 3.
Table 3
Figure BSA00000166817600052
*Nuclear phase SiO 2The microballoon mean diameter is 31 nanometers
[embodiment 15～19]
Only change used metal-salt MY nKind, all the other steps are with [embodiment 1], the character of the nucleocapsid catalyst that obtains and catalytic activity are under the same conditions listed in table 4.
Table 4
Figure BSA00000166817600061
Nuclear directly refers to nuclear phase SiO 2The microballoon mean diameter
[embodiment 20～24]
The preparation method of catalyzer is identical with [embodiment 15], only changes the mass ratio of temperature of reaction, reaction pressure, catalyzer and oxyethane, and other condition is all identical with [embodiment 15], and catalytic selectivity is as shown in table 5.
Table 5
[embodiment 25]
Mixed solution after [embodiment 15] reaction end is filtered, the catalyzer of separating is reacted under identical condition again, so reuse five times, the result shows catalyst deactivation and not obvious, as shown in table 6.
Table 6
Figure BSA00000166817600063

Claims (9)

1. one kind is used for the method that oxyethane and carbonic acid gas prepare NSC 11801, take oxyethane and carbonic acid gas as raw material, it is 50～200 ℃ in temperature of reaction, reaction pressure is 0.1～10.0MPa, the mass ratio of catalyzer and oxyethane is (0.001～1): under 1 the condition, reaction raw materials contacts the Formed vinyl acetate with catalyzer; Wherein said catalyzer is take the SiO of mean diameter as 15～500 nanometers 2Microballoon is nuclear phase, with the metal-salt MY of polymine complexing nBe the shell phase, wherein M is Ni, Zn, Cu, Fe or Co, and Y is Cl, Br or I, and n is 2 or 3; Nuclear phase SiO 2The periphery of microballoon is wrapped in the metal salt crust phase of polymine complexing, and the shell phase thickness is 0.5～8 nanometer, shell mutually in the weight ratio of polymine and metal-salt be 0.3～10, nuclear phase is 45/55～99.5/0.5 with weight ratio between the shell phase; The molecular-weight average of described polymine is 1000～20000.
2. according to claim 1ly prepare the method for NSC 11801 for oxyethane and carbonic acid gas, it is characterized in that nuclear phase SiO 2The mean diameter of microballoon is 20～450 nanometers, and the thickness of shell phase is 1～6 nanometer.
3. according to claim 2ly prepare the method for NSC 11801 for oxyethane and carbonic acid gas, it is characterized in that nuclear phase SiO 2The mean diameter of microballoon is 25～400 nanometers, and the thickness of shell phase is 1～4 nanometer.
4. according to claim 1ly prepare the method for NSC 11801 for oxyethane and carbonic acid gas, the molecular-weight average that it is characterized in that described polymine is 1000～16000.
5. according to claim 1ly prepare the method for NSC 11801 for oxyethane and carbonic acid gas, it is characterized in that the weight ratio of polymine and metal-salt was 0.3～9 during shell mutually.
6. according to claim 5ly prepare the method for NSC 11801 for oxyethane and carbonic acid gas, it is characterized in that the weight ratio of polymine and metal-salt was 0.3～8 during shell mutually.
7. according to claim 1ly prepare the method for NSC 11801 for oxyethane and carbonic acid gas, it is characterized in that the weight ratio between nuclear phase and shell are mutually is 50/50～99.2/0.8.
8. according to claim 7ly prepare the method for NSC 11801 for oxyethane and carbonic acid gas, it is characterized in that the weight ratio between nuclear phase and shell are mutually is 55/45～99/1.
9. the method for preparing NSC 11801 for oxyethane and carbonic acid gas according to claim 1, it is characterized in that temperature of reaction is 60～180 ℃, reaction pressure is 0.5～8.0MPa, and the mass ratio of catalyzer and oxyethane is (0.002～0.8): 1.
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