CN101773846A - Loaded solid alkali zeolite catalyst for synthesizing long-chain alkyl carbonate - Google Patents
Loaded solid alkali zeolite catalyst for synthesizing long-chain alkyl carbonate Download PDFInfo
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- CN101773846A CN101773846A CN200910028050A CN200910028050A CN101773846A CN 101773846 A CN101773846 A CN 101773846A CN 200910028050 A CN200910028050 A CN 200910028050A CN 200910028050 A CN200910028050 A CN 200910028050A CN 101773846 A CN101773846 A CN 101773846A
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Abstract
The invention relates to a loaded solid alkali zeolite catalyst for synthesizing long-chain alkyl carbonate, which is particularly applicable to the reaction for synthesizing the long-chain alkyl carbonate by exchanging methyl carbonate and long-chain ester with a carbon chain length more than or equal to 12. The catalyst is prepared by stirring, staying still, drying, roasting and grinding through an equal volume impregnation method with the soluble salt of alkali metal as loading substance and an HMS mesoporous molecular sieve as a carrier, and the load range is 5 to 35 percent by mass. Because of the catalyst, the yield of a reaction product long-chain alkyl carbonate is more than 78 percent, and the selectivity is more than 98 percent. In addition, the catalyst has the advantages of no pollution to the environment, no corrosion to the equipment, easy separation, recovery and preparation and the like.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of loaded solid alkali zeolite heterogeneous catalyst that is used for synthesizing long-chain alkyl carbonate by transesterification.
Background technology
Long-chain alkyl carbonate is a kind of transparent liquid or grease, have lower pour point, good lubricity, wearability, self-cleaning property, corrosion resistance, higher thermo oxidative stability, has good solubility with hydrocarbon-type oil, it is a kind of good lubricating oil base, can be widely used in the metal processing manufacturing industry, in top-grade instrument equipment, automobile etc. lubricated; Also can be applicable to industries such as weaving, cosmetics, metal degreasing, leather processing.At present less relatively to the research of this class long-chain alkyl carbonate, synthetic method mainly contains phosgenation, oxidative carbonylation method, alcoholysis of urea, ester-interchange method etc.Phosgenation exists shortcomings such as raw material severe toxicity, operation cycle length, accessory substance severe corrosion equipment, progressively is eliminated.The oxidative carbonylation method generally uses noble metal such as palladium and compound thereof to make catalyst, and employed catalyst costs an arm and a leg, the recycling difficulty of catalyst recovery, and production process operation control requires high, poor stability, and long-chain carbonic ester yield is low; The productive rate of alcoholysis of urea synthesizing bigh carbon alcohol ester is lower, and urea easily decomposes under the hot conditions.Ester-interchange method has adopted environmental protection material carbon dimethyl phthalate and aliphatic alcohol ester exchange synthesizing long-chain alkyl carbonate, can not produce pollution in the course of reaction, and reaction condition is gentle, is easy to synthesize, and productive rate is higher.
At present, the synthetic carbon chain lengths of ester-interchange method is less more than or equal to the report of 12 long-chain alkyl carbonate, and used catalyst mostly is homogeneous catalyst greatly.(Ou Yangqiu (Ou Yangqiu) such as Ou Yangqiu, Li Gang (Li Gang) .SyntheticLubricants (synthetic lubriation material) [J], 1995,22 (3) 1-5,8) prepare carbonic acid two different 13 esters with dimethyl carbonate and isotridecanol exchange, suitable catalyst is carbonate, titanate, sodium methoxide.The carbonate catalyst activity is moderate, and when its consumption was raw material gross weight 3%, product yield was 81%; The activity of titanate esters is the highest, but its facile hydrolysis, when its consumption was raw material gross weight 0.52%, product yield was 94.8%; Sodium methoxide active higher, but also facile hydrolysis, when its consumption was raw material gross weight 1.5%, product yield was 74.3%.(Qian Jinhua such as Qian Jinhua, Wang Qingyin, princes and dukes should wait. fine chemistry industry [J], 2006,23 (4): 403-406) (be called for short: DMC) catalyst with laruyl alcohol ester exchange carbonate synthesis two lauryls screens, at selected catalyst KI, KBr, K to dimethyl carbonate
2CO
3And Bu
2Among the Sn, K
2CO
3Have good activity, the conversion per pass of DMC is 59.4%, carbonic acid two lauryl productive rates 55.3%, carbonic acid two lauryl selectivity 93%.Homogeneous catalysis system exists product and catalyst separation, reclaims the problem of difficulty, and therefore, heterogeneous catalyst becomes the focus of research.Heterogeneous catalyst carbon chain lengths smaller or equal to 8 short carbon chain dialkyl carbonate ester exchange the report aspect synthetic in the majority, (Li Yongxin such as Li Yongxin, Ma Qingxiang, Chen Xingquan. petrochemical industry [J], 2005,34 (9): be catalyst 827-830), (be called for short: in reaction DPC) at propyl alcohol and dimethyl carbonate liquid phase ester exchange carbonate synthesis dipropyl with KOH/Na β, the conversion ratio of dimethyl carbonate reaches 95.5%, and the selectivity of dipropyl carbonate reaches 93.6%.Li Yongxin etc. (Li Yongxin, Zhang Yanhua, Ma Qingxiang. catalysis journal [J], 2005,26 (11): 965-970) to KNO
3/ MCM-48 is used for the catalytic performance that propyl alcohol and dimethyl carbonate carry out ester exchange carbonate synthesis dipropyl and investigates, and the conversion ratio of dimethyl carbonate can reach 99.9%, dipropyl carbonate selectivity 93.4%, productive rate 93.3%.Li Yongxin etc. (Li Yongxin, Tang Xuan, Ma Qingxiang, Tao Tao. Journal of Molecular Catalysis [J], 2006,20 (2): 125-130) studied KNO
3/ AlSBA-15 carried molecular sieve catalyst is used for the ester exchange carbonate synthesis dipropyl reaction of dimethyl carbonate and propyl alcohol, and the selectivity of dipropyl carbonate is 96.0%, and yield is 90.2%.Ren Bo etc. (appoint suddenly Li Rumin, Dong monarch. applicating technology [J], 2006,33 (11): 66-68) with CaO/ZrO
2Solid base is a catalyst, and dimethyl carbonate, isooctanol are raw material, and by ester exchange reaction carbonate synthesis di-isooctyl, experimental result shows, catalyst is at activation temperature 873K, and mass fraction is that product yield reaches 62.2% under 1.5% the condition.
Yet heterogeneous catalyst is very rare more than or equal to the report aspect 12 the long-chain alkyl carbonate at the synthetic carbon chain lengths of ester-interchange method, in CN 1785506A with the solid acid catalysis system, investigated its catalytic activity, but the author does not provide the yield of bigh carbon alcohol carbonate at synthesizing bigh carbon alcohol carbonate.The heterogeneous catalyst research of ester exchange synthesizing long-chain alkyl carbonate is also less relatively, existing heterogeneous catalyst is used for the ester exchange of short chain dialkyl carbonate mostly and synthesizes, the ester exchange heterogeneous catalyst report of long-chain alkyl carbonate is blank substantially, there is the shortcoming of preparation process complexity in solid acid catalyst, and the yield of bigh carbon alcohol carbonate is not quite clear.
Because with KNO
3, KOH is carried on the molecular sieve that short chain dialkyl carbonate synthetic had good catalytic activity, therefore, the present invention is the active component predecessor with the alkali metal salt, mesopore molecular sieve HMS is a carrier, and the loaded solid alkali zeolite catalyst of a kind of dimethyl carbonate and long-chain alkyl alcohol synthesizing long-chain alkyl carbonate by transesterification is provided.
Summary of the invention
The objective of the invention is to overcome the yield of long-chain dialkyl carbonate in the prior art and problems such as selectivity is low, catalyst separation recovery difficulty, a kind of new loaded solid alkali zeolite catalyst that is used for dimethyl carbonate and long-chain alcohol ester exchange synthesizing long-chain alkyl carbonate is provided.
A kind of loaded solid alkali zeolite catalyst that is used for synthesizing long-chain alkyl carbonate provided by the present invention, mass percent by alkali metal and mesoporous molecular sieve carrier is 5%～35%, with alkali-metal soluble-salt aqueous solution incipient impregnation mesoporous molecular sieve carrier, stir and leave standstill, drying, roasting, get through grinding.
The said alkali metal of the present invention is at least a in lithium, sodium, potassium, the caesium, alkali-metal soluble-salt comprises alkali-metal nitrate, acetate, and other soluble-salt, be mainly at least a among lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, lithium acetate, sodium acetate, potassium acetate, sodium fluoride, potassium fluoride, potash, the KI etc.
The said mesoporous molecular sieve carrier of the present invention is a HMS mesopore molecular sieve carrier, with the positive cetylamine of template agent (molecular formula: C
16H
35N is called for short: HDA), ethanol (is called for short: EtOH), H
2O presses 0.3: 7: 35 proportioning mixed dissolution, then silicon source tetraethyl orthosilicate (is called for short: TEOS) under strong agitation, slowly be added drop-wise to 0.3C
16NH
35-7EtOH-35H
2In the O mixture, form each set of dispense than being SiO
2-0.3HDA-7EtOH-35H
2O solution at room temperature continues to stir 2～24h, obtains sediment; Filtration, washing, drying at 500～700 ℃ of roasting 2～8h removed template methods, obtain HMS mesopore molecular sieve carrier then.
The present invention is 2～4h the said time of stirring, and time of repose is 2～24h.
The said baking temperature of the present invention is 90～120 ℃, and be 2～10h drying time.
The said sintering temperature of the present invention is 200～800 ℃, and roasting time is 2～8h.
The carbon chain lengths of the long-chain alkyl carbonate that the said ester-interchange method of the present invention is synthetic is more than or equal to 12.
Catalyst provided by the present invention has following characteristics than prior art:
(1) catalytic activity height.Solid alkali zeolite catalyst system and catalyzing of the present invention has higher catalytic activity with respect to general catalyst to ester exchange reaction, and the yield of long-chain dialkyl carbonate can reach more than 78%, and selectivity is all more than 98%.
(2) catalyst is easy to separate, reclaim.Homogeneous catalyst exists product to separate, reclaim the problem of difficulty, the purity of product is affected, and catalyst of the present invention very easily separates with product.
(3) catalyst preparation process is simple, and the avirulence of catalyst own, and environmentally safe is little to equipment corrosion.
The specific embodiment:
Embodiment 1
Take by weighing the positive cetylamine of 7.23g, be dissolved in the mixed solution of 40.9ml ethanol and 63.0ml water, be warming up to 40 ℃, treat that positive cetylamine dissolves fully, dropwise add the ethyl orthosilicate of 22.4ml, at room temperature continue to stir 10h, obtain sediment; Filtration, washing, drying at 600 ℃ of roasting 6h removed template methods, obtain the HMS mesopore molecular sieve then, and it is standby to put into drier.Take by weighing KNO
30.25g, be mixed with the aqueous solution, take by weighing HMS molecular sieve 4.75g again, (KNO
3Load capacity 5%) carrier HMS is added in the above-mentioned aqueous solution and to leave standstill 10h after stirring 2h, with gained sample dry 5h in 110 ℃ of baking ovens, and in Muffle furnace in 500 ℃ of following roasting 4h, take out the levigate loaded catalyst that promptly gets.Take into account in three mouthfuls of beakers of rectifying column being connected with nitrogen ingress pipe, constant pressure funnel, temperature, add prepared catalyst 0.84g, laruyl alcohol 74.5g.Wait to be warmed up to 140 ℃, begin to drip dimethyl carbonate, total addition of dimethyl carbonate is 9.07g, from beginning to drip the dimethyl carbonate calculating reacting time, reaction 4h; Constantly steam the azeotropic mixture of methyl alcohol and dimethyl carbonate in the reaction by rectifying column.Reactant liquor is analyzed with Tianjin, island GC-14B type gas chromatograph, carries out quantitative analysis with the correction normalization method, and the conversion ratio that records dimethyl carbonate is 79.9%, and the yield of carbonic acid two lauryls is 78.6%, and selectivity is 98.4%.
Embodiment 2
The Preparation of catalysts method is with embodiment 1, modulation KNO
3Load capacity on carrier HMS makes KNO
3Load capacity be 10%.The analytical method of reaction condition and product is with embodiment 1, and activity of such catalysts result is as follows: the conversion ratio of dimethyl carbonate is 85.4%, and the yield of carbonic acid two lauryls is 84.0%, and selectivity is 98.4%.
Embodiment 3
The Preparation of catalysts method is with embodiment 1, modulation KNO
3Load capacity on carrier HMS makes KNO
3Load capacity be 15%.The analytical method of reaction condition and product is with embodiment 1, and activity of such catalysts result is as follows: the conversion ratio of dimethyl carbonate is 87.0%, and the yield of carbonic acid two lauryls is 86.7%, and selectivity is 99.7%.
Embodiment 4
The Preparation of catalysts method is with embodiment 1, modulation KNO
3Load capacity on carrier HMS makes KNO
3Load capacity be 20.0%.The analytical method of reaction condition and product is with embodiment 1, and activity of such catalysts result is as follows: the conversion ratio of dimethyl carbonate is 83.8%, and the yield of carbonic acid two lauryls is 82.6%, and selectivity is 98.6%.
Embodiment 5
The Preparation of catalysts method is with embodiment 1, and the predecessor of modulation active component is K (OAc)
2, load capacity is 10%.The analytical method of reaction condition and product is with embodiment 1, and activity of such catalysts result is as follows: the conversion ratio of dimethyl carbonate is 80.5%, and the yield of carbonic acid two lauryls is 79.5%, and selectivity is 98.7%.
Embodiment 6
The Preparation of catalysts method is with embodiment 1, and the predecessor of modulation active component is KF, and load capacity is 15%.The analytical method of reaction condition and product is with embodiment 1, and activity of such catalysts result is as follows: the conversion ratio of dimethyl carbonate is 87.2%, and the yield of carbonic acid two lauryls is 85.8%, and selectivity is 98.3%.
Embodiment 7
The Preparation of catalysts method is with embodiment 1, and the predecessor of modulation active component is K
2CO
3, load capacity is 13%.The analytical method of reaction condition and product is with embodiment 1, and activity of such catalysts result is as follows: the conversion ratio of dimethyl carbonate is 79.9%, and the yield of carbonic acid two lauryls is 79.2%, and selectivity is 99.1%.
Embodiment 8
Preparation of catalysts is with embodiment 1, and the carbon number of modulation long-chain alcohol is a raw material with positive hexadecanol, takes into account in three mouthfuls of beakers of rectifying column being connected with nitrogen ingress pipe, constant pressure funnel, temperature, adds prepared catalyst 1.06g, positive hexadecanol 96.98g.Wait to be warmed up to 160 ℃, begin to drip dimethyl carbonate, total addition of dimethyl carbonate is 9.07g, from beginning to drip the dimethyl carbonate calculating reacting time, reaction 4h; Constantly steam the azeotropic mixture of methyl alcohol and dimethyl carbonate in the reaction by rectifying column.Reactant liquor is analyzed with Tianjin, island GC-14B type gas chromatograph, carries out quantitative analysis with the correction normalization method, and the conversion ratio that records dimethyl carbonate is 82.4%, and the yield of carbonic acid two lauryls is 81.1%, and selectivity is 98.5%.
Claims (7)
1. loaded solid alkali zeolite catalyst that is used for synthesizing long-chain alkyl carbonate, it is characterized in that: the mass percent by alkali-metal soluble-salt and mesoporous molecular sieve carrier is 5%～35%, with alkali-metal soluble-salt aqueous solution incipient impregnation mesoporous molecular sieve carrier, stir and leave standstill, drying, roasting, get through grinding.
2. the loaded solid alkali zeolite catalyst that is used for synthesizing long-chain alkyl carbonate according to claim 1, it is characterized in that: described alkali-metal soluble-salt comprises alkali-metal nitrate, acetate and other soluble-salt, is mainly at least a among lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, lithium acetate, sodium acetate, potassium acetate, sodium fluoride, potassium fluoride, potash, the KI etc.
3. the loaded solid alkali zeolite catalyst that is used for synthesizing long-chain alkyl carbonate according to claim 1 is characterized in that: described mesoporous molecular sieve carrier is a HMS mesopore molecular sieve carrier, with the positive cetylamine of template agent (molecular formula: C
16H
35N is called for short: HDA), ethanol (is called for short: EtOH), H
2O presses 0.3: 7: 35 proportioning mixed dissolution, then silicon source tetraethyl orthosilicate (is called for short: TEOS) under strong agitation, slowly be added drop-wise to 0.3C
16NH
35-7EtOH-35H
2In the O mixture, form each set of dispense than being SiO
2-0.3HDA-7EtOH-35H
2O solution at room temperature continues to stir 2～24h, obtains sediment; Filtration, washing, drying at 500～700 ℃ of roasting 2～8h removed template methods, obtain HMS mesopore molecular sieve carrier then.
4. the loaded solid alkali zeolite catalyst that is used for synthesizing long-chain alkyl carbonate according to claim 1 is characterized in that: the time of stirring is 2～4h, and time of repose is 2～24h.
5. the loaded solid alkali zeolite catalyst that is used for synthesizing long-chain alkyl carbonate according to claim 1 is characterized in that: baking temperature is 90～120 ℃, and be 2～10h drying time.
6. the loaded solid alkali zeolite catalyst that is used for synthesizing long-chain alkyl carbonate according to claim 1 is characterized in that: sintering temperature is 200～800 ℃, and roasting time is 2～8h.
7. the loaded solid alkali zeolite catalyst that is used for synthesizing long-chain alkyl carbonate according to claim 1 is characterized in that: wherein the carbon chain lengths of the synthetic long-chain alkyl carbonate of ester-interchange method is more than or equal to 12.
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| CN103191768A (en) * | 2013-03-22 | 2013-07-10 | 南京工业大学 | Mesoporous solid strong-alkaline catalyst and preparation method and application of catalyst |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102139224A (en) * | 2010-12-29 | 2011-08-03 | 齐齐哈尔大学 | Catalyst for low-temperature gaseous phase synthesis of benzaldehyde and preparation method thereof |
| CN102139224B (en) * | 2010-12-29 | 2013-07-17 | 齐齐哈尔大学 | Catalyst for low-temperature gaseous phase synthesis of benzaldehyde and preparation method thereof |
| CN103191768A (en) * | 2013-03-22 | 2013-07-10 | 南京工业大学 | Mesoporous solid strong-alkaline catalyst and preparation method and application of catalyst |
| CN108727578A (en) * | 2018-03-15 | 2018-11-02 | 中国科学院成都有机化学有限公司 | A kind of preparation method of isobide base makrolon |
| CN109337058A (en) * | 2018-09-11 | 2019-02-15 | 浙江恒澜科技有限公司 | A kind of preparation method and application of environment-friendly type polyester titanium complex catalyst |
| CN114505090A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Catalyst for preparing isosorbide and synthetic method and application thereof |
| CN114505090B (en) * | 2020-10-28 | 2024-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing isosorbide and synthetic method and application thereof |
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Application publication date: 20100714 |