CN103418440B - The catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate - Google Patents
The catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate Download PDFInfo
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- CN103418440B CN103418440B CN201210150481.5A CN201210150481A CN103418440B CN 103418440 B CN103418440 B CN 103418440B CN 201210150481 A CN201210150481 A CN 201210150481A CN 103418440 B CN103418440 B CN 103418440B
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- catalyst
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- ethylene carbonate
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a kind of catalyst for preparing ethyl glycol by hydrolysis of ethylene carbonate, mainly solve the problem of the catalyst poor water resistance existed in conventional art.The present invention comprises following component by adopting with weight parts: a) heteropoly acid of 0.1 ~ 50 part; B) carrier of 50 ~ 99.9 parts; Wherein, carrier is selected from SiO
2, at least one in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or diatomite, and through containing the process of hetero atom esters of silicon acis; Described is C containing hetero atom esters of silicon acis
xh
ya
z-Si (OR)
3, wherein A is N or P, x=1 ~ 10, y=4 ~ 26, z=1 ~ 5, R is CH
3or C
2h
5technical scheme solve this problem preferably, can be used in the industrial production of preparing ethyl glycol by hydrolysis of ethylene carbonate.
Description
Technical field
The present invention relates to a kind of catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate.
Background technology
The hydrolysis of ester class is a kind of important chemical reaction, is widely used in the every field of petrochemical iy produced, wherein cyclic carbonate, and the hydrolysis as ethylene carbonate (EC), propene carbonate etc. has very important fundamental position especially.
The hydrolysis of EC is the important step of being produced ethylene glycol (EG) by oxirane (EO) catalysis hydration two-step method.EG is a kind of important Organic Chemicals, is mainly used to produce polyester fiber, antifreezing agent, unsaturated polyester resin, non-ionic surface active agent, monoethanolamine and explosive etc.The production technology of EG is mainly divided into petrochemical industry route and non-petrochemical industry route.In petrochemical industry route, have EO direct hydration method and EO catalytic hydration, direct hydration method needs higher water ratio (being greater than 20) guarantee to have higher EG yield, and it is higher to consume energy in the process of the EG that purifies.EO catalytic hydration comprises again direct catalytic hydration and EC route.Direct catalytic hydration water than relatively low (about about 5), but still needs to evaporate a large amount of water of removing, and first EC route then utilizes the CO discharged during ethylene EO
2for raw material and EO generate EC under the effect of catalyst, be then that intermediate product catalyzing hydrolysis generates EG with EC, this process water, than close to stoichiometric proportion 1, is the industrialization direction of EO EG from now on.
Mainly contain for the catalyst of annular carbonic acid esters hydrolysis at present: compound (JP822106631,1982 of alkali (soil) metal carbonate (hydrogen) salt (US4524224,1985), Mo and W; WO2009071651,2009), quaternary ammonium salt, quaternary alkylphosphonium salt and ion exchange resin (EP0133763,1989; US6080897,2000; US20090156867,2009) etc.But more or less there is catalyst separation difficulty in these catalyst system and catalyzings, activity is low, stability is not high, severe reaction conditions, poor water resistance and the problem such as catalyst cost is higher.
Heteropoly acid is owing to having higher catalytic activity, and not easy in inactivation, be therefore widely used in catalytic reaction.To loaded by heteropoly acid and carrier can increase its surface area and suitable pore structure is provided, and homogeneous catalyst can be made supported.But the greatest problem that the heteropolyacid catalyst of load exists is the easy solution-off of its active component heteropoly acid, thus catalytic activity is caused to decline (petrochemical industry, 2007,36 (12): 1220-1224).
Summary of the invention
Technical problem to be solved by this invention is the problem of the catalyst poor water resistance existed in conventional art, provides a kind of catalyst of new ethylene carbonate Ester hydrolysis preparing ethylene glycol.This catalyst has heteropoly acid not easily from solution-off carrier, the feature that catalyst stability is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate, comprises following component with weight parts
A) heteropoly acid of 0.1 ~ 50 part;
B) carrier of 50 ~ 99.9 parts;
Wherein, carrier is selected from SiO
2, at least one in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or diatomite, and through containing the process of hetero atom esters of silicon acis; Described is C containing heteroatomic esters of silicon acis
xh
ya
z-Si (OR)
3, wherein A is N or P, x=1 ~ 16, y=4 ~ 26, z=1 ~ 5, R is CH
3or C
2h
5.
In technique scheme, the treatment temperature preferable range containing hetero atom esters of silicon acis is 70 ~ 140 DEG C, and more preferably scope is 90 ~ 120 DEG C; Processing time preferable range is 1 ~ 60 hour, and more preferably scope is 5 ~ 48 hours.Containing hetero atom esters of silicon acis and SiO
2the weight ratio preferable range of carrier is 0.005 ~ 0.15: 1, and more preferably scope is 0.01 ~ 0.1: 1.The surface area of carrier is 100 ~ 1500m
2/ g, is preferably 200 ~ 1000m
2/ g.With weight parts, the consumption preferable range of heteropoly acid is 1 ~ 40 part, SiO
2the consumption preferable range of carrier is 60 ~ 99 parts.Described heteropoly acid is the heteropoly acid of structure with Keggin, is selected from least one in phosphotungstic acid, silico-tungstic acid, germanotungstic acid, arsenowolframic acid, phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid.
The preparation method of catalyst used in the present invention is as follows:
1. by carrier, process in 110 DEG C of temperature Toluene solution containing hetero atom esters of silicon acis after, filter, in 110 DEG C of dried overnight after the solid ethanol of gained washs 3 times.
2. by the carrier S iO containing the process of hetero atom esters of silicon acis of step 1 gained
2be placed in the ethanolic solution containing aequum heteropoly acid, after room temperature places 3h, at 25 ~ 60 DEG C of slow evaporates to dryness, the solid of gained is in 110 DEG C of dried overnight.
Carrier used in the present invention is used containing after the process of hetero atom esters of silicon acis, containing hetero atom alkalescent group on surface graft, utilize this alkalescent group can fix acid heteropoly acid molecule, thus while immobilized heteropoly acid, also improve the stability of catalyst, prevent heteropoly acid in the loss of course of reaction.Catalyst of the present invention is used in the reaction of ethylene carbonate Ester hydrolysis, reaction temperature 100 DEG C, the mol ratio of water and ethylene carbonate is 1.5: 1, the weight ratio of catalyst and ethylene carbonate is under 0.05: 1 condition, the conversion ratio of ethylene carbonate can reach 98.7%, and the selective of ethylene glycol reaches 99.7%, after catalyst reuses 5 times, activity decrease is less than 5%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
By carrier (Degussa, Aerisol 200, surface area 210m
2/ g) 10.0g is placed in 500mL three-necked bottle, then adds 200mL dry toluene respectively, 2.0mL APTES (3-aminopropyltriethoxysilane, APTES, C
3h
8nSi (OC
2h
5)
3), filter after 110 DEG C of backflow 24h, with after absolute ethanol washing 3 times in 110 DEG C of baking ovens dry 12h, then obtained solid is added in the 100mL ethanol solution containing phosphotungstic acid 2.0g, after room temperature leaves standstill 3h, 50 DEG C of slow evaporates to dryness, dried overnight in 110 DEG C of baking ovens, obtains catalyst.
[embodiment 2 ~ 9]
With [embodiment 1], just the kind of heteropoly acid and the kind of consumption, carrier and consumption, the kind containing hetero atom esters of silicon acis, consumption, treatment temperature are different with the processing time.Specifically in table 1.
Table 1
aconsumption containing hetero atom esters of silicon acis refers to containing hetero atom esters of silicon acis and SiO
2the weight ratio of carrier.
btPDT:Trimethoxysilyl propyldiethylenetriamine (the silica-based propyl group diethyl triamine of trimethoxy), structural formula is C
7h
18n
3si (OCH
3)
3.
ctPED:N-[3-(trimethoxysilyl)-propylethylene] diamine (N-[3-(trimethoxy is silica-based)-ethyl] diamines), structural formula is C
5h
13n
2si (OCH
3)
3.
ddPPTS:3-diphenylphosphino propyltriethoxy silane (3-diphenylphosphino-1-triethoxysilane), structural formula is C
15h
16pSi (OC
2h
5)
3.
[embodiment 10 ~ 18]
Catalyst prepared by 44.0 grams of ethylene carbonates, 13.5 grams of deionized waters and 2.2 grams [embodiment 1 ~ 9] is placed in 100 milliliters of autoclaves, and (mol ratio of water and ethylene carbonate is 1.5, the ratio of catalyst and ethylene carbonate is 0.05), 100 DEG C are reacted 2 hours.After reaction terminates, autoclave is cooled to room temperature, emptying.Get liquid product and carry out gas chromatographic analysis, result is as shown in table 2.
Table 2
[embodiment 19]
With [embodiment 10], just reaction temperature is 120 DEG C.The conversion ratio obtaining ethylene carbonate is 95.9%, and the selective of ethylene glycol is 96.5%, and other is many ethylene glycol.
[embodiment 20]
With [embodiment 10], just the quality of deionized water is 27.0 grams (mol ratio of water and ethylene carbonate is 3).Obtaining ethylene carbonate ester conversion rate is 90.8%, and the selective of ethylene glycol is 99.1%, and other is many ethylene glycol.
[embodiment 21]
With [embodiment 10], just catalyst is catalyst prepared by [embodiment 1], and consumption is 1.1 grams (ratio of catalyst and ethylene carbonate is 0.025).Obtaining ethylene carbonate ester conversion rate is 59.8%, and the selective of ethylene glycol is 98.2%, and other is many ethylene glycol.
[embodiment 22]
Catalyst after [embodiment 12] reaction being terminated applies mechanically 5 times by same reaction conditions, and activity does not obviously decline.Reaction result is shown in Table 3.
Table 3
[comparative example 1 ~ 9]
By SiO used in [embodiment 1 ~ 9]
2material is without containing the process of hetero atom esters of silicon acis, and check and rate with [embodiment 10], reaction result is in table 4.
Table 4
[comparative example 10]
Catalyst after reaction in comparative example 3 being terminated applies mechanically 5 times by same reaction conditions, and the reaction result of gained is as shown in table 5.
Table 5
Claims (4)
1. a catalyst for preparing ethyl glycol by hydrolysis of ethylene carbonate, comprises following component with weight parts
A) heteropoly acid of 0.1 ~ 50 part;
B) carrier of 50 ~ 99.9 parts;
Wherein, carrier is selected from SiO
2, at least one in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or diatomite, and through containing the process of hetero atom esters of silicon acis; Described is C containing hetero atom esters of silicon acis
xh
ya
z-Si (OR)
3, wherein A is P, x=1 ~ 16, y=4 ~ 26, z=1 ~ 5, R is C
2h
5;
Wherein, the treatment temperature containing hetero atom esters of silicon acis is 70 ~ 140 DEG C, and the processing time is 1 ~ 60 hour, containing hetero atom esters of silicon acis and SiO
2the weight ratio of carrier is 0.005 ~ 0.15:1;
The surface area of carrier is 100 ~ 1500m
2/ g;
Heteropoly acid is selected from least one in germanotungstic acid, arsenowolframic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid.
2. the catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate according to claim 1, it is characterized in that the treatment temperature containing hetero atom esters of silicon acis is 90 ~ 120 DEG C, the processing time is 5 ~ 48 hours, containing hetero atom esters of silicon acis and SiO
2the weight ratio of carrier is 0.01 ~ 0.1:1.
3. the catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate according to claim 1, is characterized in that the surface area of carrier is 200 ~ 1000m
2/ g.
4. the catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate according to claim 1, is characterized in that with weight parts, and the consumption of heteropoly acid is 1 ~ 40 part, SiO
2the consumption of carrier is 60 ~ 99 parts.
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| CN103418440B true CN103418440B (en) | 2015-08-12 |
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| CN107915576B (en) * | 2016-10-08 | 2021-03-30 | 中国石油化工股份有限公司 | Method for producing ethylene glycol by ethylene carbonate hydrolysis |
| CN107915578B (en) * | 2016-10-08 | 2021-02-09 | 中国石油化工股份有限公司 | Method for producing ethylene glycol by ethylene carbonate hydrolysis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283580A (en) * | 1979-05-24 | 1981-08-11 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Process for the production of alkylene glycols |
| CN1978415A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Method for preparing ethyl glycol by hydrolysis of ethylene carbonate |
| CN101618349A (en) * | 2009-07-06 | 2010-01-06 | 江南大学 | Preparation method of heteropoly acid catalysts by taking organic modified concave-convex soil as carrier |
| CN101733163A (en) * | 2009-12-16 | 2010-06-16 | 哈尔滨师范大学 | Method for preparing polyacid crystal catalyst |
-
2012
- 2012-05-16 CN CN201210150481.5A patent/CN103418440B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283580A (en) * | 1979-05-24 | 1981-08-11 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Process for the production of alkylene glycols |
| CN1978415A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Method for preparing ethyl glycol by hydrolysis of ethylene carbonate |
| CN101618349A (en) * | 2009-07-06 | 2010-01-06 | 江南大学 | Preparation method of heteropoly acid catalysts by taking organic modified concave-convex soil as carrier |
| CN101733163A (en) * | 2009-12-16 | 2010-06-16 | 哈尔滨师范大学 | Method for preparing polyacid crystal catalyst |
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