CN103028404A - Catalyst for preparing ethylene carbonate by using ethylene oxide and carbon dioxide - Google Patents

Catalyst for preparing ethylene carbonate by using ethylene oxide and carbon dioxide Download PDF

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CN103028404A
CN103028404A CN2011102997656A CN201110299765A CN103028404A CN 103028404 A CN103028404 A CN 103028404A CN 2011102997656 A CN2011102997656 A CN 2011102997656A CN 201110299765 A CN201110299765 A CN 201110299765A CN 103028404 A CN103028404 A CN 103028404A
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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 catalyst for preparing ethylene carbonate by using ethylene oxide and carbon dioxide, mainly aiming at solving the problems that the activity of the existing catalyst is low and the active components are apt to lose in the prior art. The catalyst comprises the following components in parts by weight: a component A: 10-80 parts of metal silicate which is loaded on SiO2 carriers, wherein the weight of the metal silicate is 1-50 percent of the total weight of the component A; and a component B: 20-90 parts of SiO2 which is grafted with alkyl ester silicate CaHbXcSi(OR)3, wherein a is equal to 3-23, b is equal to 7-33, c is equal to 1-3, X is N, P or S, R is -CH3 or -CH2CH3, and the weight ratio of the grafted alkyl ester silicate to the SiO2 is (0.002-0.15):1. By adopting the technical scheme, the problems are better solved and the catalyst can be used for the industrial production of the ethylene carbonate which is prepared by using the ethylene oxide and the carbon dioxide.

Description

Oxirane and carbon dioxide prepare the catalyst of ethylene carbonate
Technical field
The present invention relates to the catalyst that a kind of oxirane and carbon dioxide prepare ethylene carbonate.
Background technology
Ethylene carbonate is a kind of solvent and fine-chemical intermediate of function admirable, is the potential basic material of organic chemical industry.While CO 2Be a kind of greenhouse gases, how effectively fixingly become one of challenging problem of tool in this century, and by oxirane and CO 2The reaction synthesizing ethylene carbonate is exactly a kind of good fixing means wherein.Along with recently take ethylene carbonate as the raw material co-producing dimethyl carbonate and glycol reaction day by day receive publicity, by cyclic carbonate fixation of C O 2Approach also be subject to increasing attention.
The method majority of the production cyclic carbonate 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 complex, employed Lewis alkali has organic base (such as DMF, DMAP etc.), quaternary ammonium salt, quaternary alkylphosphonium salt, imidazole salts, crown ether etc.These catalyst system and catalyzings are perhaps active, selectively not high, perhaps used the very strong organic solvent of toxicity, and the shortcoming that exists catalyst to be difficult to separate of homogeneous catalysis system.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 time is longer.Xia Chungu etc. are with ZnCl 2Immobilized on chitin carrier, although obtained higher catalytic activity, catalyst has been applied mechanically after 5 times activity decreaseds approximately 8%, infers 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, activity is high, reaction condition is gentle, the catalyst system and catalyzing that is difficult for inactivation seems 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 component easily runs off, the catalyst that provides a kind of new oxirane and carbon dioxide to prepare ethylene carbonate.It is high that this catalyst has catalytic activity, 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 oxirane and carbon dioxide prepare the catalyst of ethylene carbonate, comprise following component in parts by weight:
Component A:10～80 part be carried on SiO 2Metal silicate on the carrier, wherein metal silicate weight is 1～50% of component A gross weight;
The grafting of component B:20～90 part alkyl silicate C aH bX cSi (OR) 3SiO 2A=3～23 wherein, b=7～33, c=1～3, X is N, P or S, R is-CH 3Or-CH 2CH 3, the alkyl silicate in the grafting and SiO 2Weight ratio be (0.002～0.15): 1.
In the technique scheme, in parts by weight, the consumption preferable range of component A is 15～75 parts, and more preferably scope is 20～70 parts; Wherein metal silicate weight more preferably scope be 5～45% of component A gross weight, more preferably scope is 10～40% of component A gross weight.The consumption preferable range of component B is 25～85 parts, and more preferably scope is 30～80 parts; The wherein alkyl silicate in the grafting and SiO 2The weight ratio preferable range be (0.005～0.15): 1, more preferably scope (0.01～0.15): 1.Described metal silicate preferred version is to be selected from least a in cupric silicate, zinc silicate, cobaltous silicate or the silicic acid nickel.SiO among component A and the component B 2Preferred version is for all being selected from commercial SiO 2, at least a in micropore pure silicon molecular sieve or the mesoporous pure silicon molecular sieve, more preferably scheme is for being selected from commercial SiO 2, a kind of in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or the diatomite.SiO among component A and the component B 2The specific area preferable range be 20～1500 meters 2/ gram, more preferably scope is 40～1000 meters 2/ gram, most preferred range is 50～800 meters 2/ gram.
Commercial SiO among the present invention 2Can be Degussa Aerisol 200, Degussa OX50 or Degussa AD380.
The preparation method of catalyst of the present invention may further comprise the steps:
A) slaine of cupric, zinc, cobalt or nickel is soluble in water, to the precipitating reagent that wherein adds aequum and SiO 2, 75～95 ℃ were stirred 1～10 hour, and were precipitated thing; After the washing of gained sediment, drying, namely obtain component A;
Wherein said precipitating reagent is selected from urea, and described slaine can be metal nitrate, hydrochloride, bromine salt, salt compounded of iodine, sulfate, disulfate, phosphate, hydrophosphate or dihydric phosphate.
B) will contain heteroatomic alkyl silicate C aH bX cSi (OR) 3Be dissolved in the organic solvent, to wherein adding SiO 2, stirring and refluxing 10～30 hours obtains mixture; The gained mixture namely obtains component B after washing, drying; Wherein said organic solvent is selected from toluene, benzonitrile or ethylbenzene.
C) component A and component B are ground to respectively greater than evenly mixing behind 200 orders, namely obtain catalyst of the present invention.
The present invention is immobilized in SiO with the form of silicate with reactive metal 2On, adopt simultaneously grafting will contain efficiently heteroatomic alkyl silicate and be evenly dispersed in SiO 2Then evenly mix both on the surface, and the composite catalyst activity that so forms is high, good stability.The present invention is with ZnSiO 3/ SBA-15 and DPPTS/SiO 2Being composite catalyst, is 0.033: 1 at the mass ratio of composite catalyst and oxirane, and reaction temperature is 120 ℃, CO 2Reaction was 3 hours when pressure was 2.0MPa, and the yield of ethylene carbonate can reach 97%, and catalyst 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.
The specific embodiment
[embodiment 1]
In 1000 ml beakers, add and contain 24.3 gram Cu (NO 3) 2300 milliliters of the aqueous solution, then add SiO 2(Degussa, Aerisol 200,194 meters of specific areas for carrier 100.0 grams 2/ restrain) and urea 34.2 grams, under agitation be warming up to 90 ℃, and kept 2 hours, then filter, after deionized water washing 3 times, in 120 ℃ of baking ovens, spend the night, the solid of gained is called A1.Measure through ICP-AES, wherein Cu is with CuSiO 3The weight ratio that meter accounts for A1 is 15.8%.
[embodiment 2]
With [embodiment 1], be Cu (NO in the solution 3) 2Consumption be 58.5 the gram, SiO 2Carrier is Degussa OX50, and specific area is 50 meters 2/ gram, the consumption of urea are 82.7 grams, are warming up to 80 ℃ and kept 9 hours, and the solid of gained is called A2.Measure through ICP-AES, wherein Cu is with CuSiO 3The weight ratio that meter accounts for A2 is 38.2%.
[embodiment 3]
With [embodiment 1], be Cu (NO in the solution 3) 2Consumption be 6.72 the gram, SiO 2Carrier is Silica-1, and its specific area is 526 meters 2/ gram, the consumption of urea are 9.5 grams, and the solid of gained is called A3.Measure through ICP-AES, wherein Cu is with CuSiO 3The weight ratio that meter accounts for A3 is 4.5%.
[embodiment 4]
With [embodiment 1], just with Cu (NO 3) 2Solution changes Zn (NO into 3) 2Solution, SiO 2Carrier is SBA-15, and its specific area is 680 meters 2/ gram, the solid that obtains is called A4.Measure through ICP-AES, wherein Zn is with ZnSiO 3The weight ratio that meter accounts for A4 is 15.2%.
[embodiment 5]
With [embodiment 1], just with Cu (NO 3) 2Solution changes ZnCl into 2Solution, SiO 2Carrier is MCM-41, and its specific area is 1032 meters 2/ gram, the solid that obtains is called A5.Measure through ICP-AES, wherein Zn is with ZnSiO 3The weight ratio that meter accounts for A5 is 22.6%.
[embodiment 6]
With [embodiment 1], just with Cu (NO 3) 2Solution changes ZnSO into 4Solution, the solid that obtains is called A6.Measure through ICP-AES, wherein Zn is with ZnSiO 3The weight ratio that meter accounts for A6 is 17.8%.
[embodiment 7]
With [embodiment 1], just with Cu (NO 3) 2Solution changes Ni (NO into 3) 2Solution, the solid that obtains is called A7.Measure through ICP-AES, wherein Ni is with NiSiO 3The weight ratio that meter accounts for A7 is 15.4%.
[embodiment 8]
With [embodiment 1], just with Cu (NO 3) 2Solution changes Co (NO into 3) 2Solution, the solid that obtains is called A8.Measure through ICP-AES, wherein Co is with CoSiO 3The weight ratio that meter accounts for A8 is 15.9%.
[embodiment 9]
With SiO 2(Degussa, Aerisol 200,194 meters of specific areas for carrier 2/ gram) 100.0 grams place 1000 milliliters of three-necked bottles, then add respectively 400 milliliters of dry toluenes, 40.0 gram APTES (3-aminopropyltriethoxysilane, APTES, structural formula C 3H 8NSi (OC 2H 5) 3), filter after 24 hours 110 ℃ of backflows, use absolute ethanol washing, after 80 ℃ of dried overnight, weigh, find APTES weight and SiO in the grafting 2Weight ratio be 0.051: 1, the solid that obtains is called B1.
[embodiment 10]
With [embodiment 9], just the addition of APTES is 5.0 grams, found that APTES weight and SiO that grafting is got on 2Weight ratio be 0.011: 1, the solid that obtains is called B2.
[embodiment 11～15]
Change employed SiO 2Kind, all the other preparation conditions are all identical with [embodiment 9], specifically see Table 1.
Table 1
[embodiment 16～19]
Change and employedly contain heteroatomic alkyl silicate kind, and employed SiO 2(specific area is 385 meters for Degussa AD380 2/ gram), all the other preparation conditions are all identical with [embodiment 9], specifically see Table 2.
Table 2
Figure BDA0000096356710000052
A:TPED:N-[3-(trimethoxysilyl)-propylethylene] and diamine (N-[3-(trimethoxy is silica-based)-propyl group ethyl] diamines), structural formula is C 5H 13N 2Si (OCH 3) 3
B:TPDT:Trimethoxysilyl propyldiethylenetriamine (the silica-based propyl group diethyl triamine of trimethoxy), structural formula is C 7H 18N 3Si (OCH 3) 3
C:MPTS:mercaptopropyltrimethoxy silane (mercaptopropyl trimethoxysilane), structural formula are C 3H 7SSi (OCH 3) 3
D:DPPTS:3-diphenylphosphino propyltriethoxy silane (3-diphenylphosphino-1-triethoxysilane), structural formula is C 15H 16PSi (OC 2H 5) 3
[embodiment 20]
Be ground to respectively greater than mechanical mixture behind 200 orders 2.0 gram A1 and 17.0 gram B1 even, obtain composite catalyst.This composite catalyst is in parts by weight, contains altogether to be carried on carrier S iO 2On 10.5 parts of metal silicates, grafting contain the SiO of hetero atom alkyl silicate 289.5 part.This composite catalyst is used for the reaction of oxirane and carbon dioxide, condition is as follows: add 150.0 gram oxirane and 5.0 gram composite catalysts in 300 milliliters of autoclaves, be filled with 1.0MPaCO 2, be warming up to 120 ℃, be filled with again CO 2, keep reaction pressure at 2.0MPa, react and remove by filter catalyst after 3 hours, recording the oxirane conversion ratio is 23.3%, and ethylene carbonate selectively is 96.7%, and the ethylene carbonate yield is 22.5%.
[embodiment 21～32]
The A series component of different proportion is pressed identical method mechanical mixture with B series component, and reaction condition the results are shown in Table 3 with [embodiment 20].
Table 3
Figure BDA0000096356710000061
C EO%: the conversion ratio of oxirane
S EC%: ethylene carbonate selective
X EC%: the yield of ethylene carbonate
[embodiment 33]
Mixed liquor after [embodiment 31] reaction end is filtered, the catalyst of separating is reacted under identical condition again, so reuse five times, the result shows the catalyst activity loss less than 5%, and is as shown in table 4.
Table 4
Figure BDA0000096356710000071

Claims (8)

1. an oxirane and carbon dioxide prepare the catalyst of ethylene carbonate, comprise following component in parts by weight:
Component A:10～80 part be carried on SiO 2Metal silicate on the carrier, wherein metal silicate weight is 1～50% of component A gross weight;
The grafting of component B:20～90 part alkyl silicate C aH bX cSi (OR) 3SiO 2A=3～23 wherein, b=7～33, c=1～3, X is N, P or S, R is-CH 3Or-CH 2CH 3, the alkyl silicate in the grafting and SiO 2Weight ratio be (0.002～0.15): 1.
2. oxirane according to claim 1 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that in parts by weight, and the consumption of component A is 15～75 parts, and wherein metal silicate weight is 5～45% of component A gross weight; The consumption of component B is 25～85 parts, wherein the alkyl silicate in the grafting and SiO 2Weight ratio be (0.005～0.15): 1.
3. oxirane according to claim 2 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that in parts by weight, and the consumption of component A is 20～70 parts, and wherein metal silicate weight is 10～40% of component A gross weight; The consumption of component B is 30～80 parts, wherein the alkyl silicate in the grafting and SiO 2Weight ratio be (0.01～0.15): 1.
4. oxirane according to claim 1 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that described metal silicate is selected from least a in cupric silicate, zinc silicate, cobaltous silicate or the silicic acid nickel.
5. oxirane according to claim 1 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that the SiO among component A and the component B 2All be selected from commercial SiO 2, at least a in micropore pure silicon molecular sieve or the mesoporous pure silicon molecular sieve.
6. oxirane according to claim 5 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that the SiO among component A and the component B 2All be selected from commercial SiO 2, a kind of in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or the diatomite.
7. oxirane according to claim 1 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that the SiO among component A and the component B 2Specific area be 20～1500 meters 2/ gram.
8. oxirane according to claim 7 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that the SiO among component A and the component B 2Specific area be 40～1000 meters 2/ gram.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109331838A (en) * 2018-10-09 2019-02-15 华侨大学 A kind of preparation method of the super-hydrophobic catalytic film of noble metal@silicic acid nickel
CN111790438A (en) * 2020-07-06 2020-10-20 中国科学院山西煤炭化学研究所 Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof
CN112823883A (en) * 2019-11-20 2021-05-21 万华化学集团股份有限公司 Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109331838A (en) * 2018-10-09 2019-02-15 华侨大学 A kind of preparation method of the super-hydrophobic catalytic film of noble metal@silicic acid nickel
CN109331838B (en) * 2018-10-09 2021-04-30 华侨大学 Preparation method of noble metal @ nickel silicate super-hydrophobic catalytic film
CN112823883A (en) * 2019-11-20 2021-05-21 万华化学集团股份有限公司 Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof
CN112823883B (en) * 2019-11-20 2022-07-12 万华化学集团股份有限公司 Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof
CN111790438A (en) * 2020-07-06 2020-10-20 中国科学院山西煤炭化学研究所 Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof
CN111790438B (en) * 2020-07-06 2021-12-03 中国科学院山西煤炭化学研究所 Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof

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