CN107537552A - A kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst - Google Patents
A kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst Download PDFInfo
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- CN107537552A CN107537552A CN201710845632.1A CN201710845632A CN107537552A CN 107537552 A CN107537552 A CN 107537552A CN 201710845632 A CN201710845632 A CN 201710845632A CN 107537552 A CN107537552 A CN 107537552A
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- oxalate
- ethylene glycol
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- monomethyl ether
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Abstract
The invention discloses a kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst, mainly solves the shortcomings that traditional catalyst preparation technology is complicated, glycol monoethyl ether is selectively low, poor catalyst stability.Catalyst of the present invention is made by sol-gal process, a) is mixed using methyl silicate, tetraethyl orthosilicate or polysilicates are a kind of at least within ethanol；B) one kind at least within added in five water copper nitrates, copper sulphate, copper acetate continues stirring 0.5 5 hours；C) one kind at least within added in above-mentioned solution in ZSM 5, MCM 22,56 former powder of MCM continues to stir；By step c）In obtained solution obtain the technical scheme of glycol monoethyl ether catalyst through gel, aging, drying, roasting, disadvantages mentioned above is efficiently solved, in the industrial production that can be widely used for glycol monoethyl ether.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalysis
The preparation method of agent.
Background technology
The resource general layout in China can be summarized as oil starvation, few gas, more coals at present.Cleaning coal chemical industry can not only make full use of coal
Charcoal resource, the waste gas discharge that coal directly burns is reduced, significantly mitigates environmental pressure, to keeping energy security and environmental protection
It is all highly beneficial, it is unusual important field of research.For energy resource consumption is very big, for China of petroleum resources critical shortage,
Its meaning is more prominent.
Glycol monoethyl ether is a kind of important chemicals, colourless transparent liquid, has pleasant smell.With water,
Ethanol, ether, glycerine, acetone, DMF are miscible.As paint solvent, bleeding agent, levelling agent and organic synthesis
Intermediate, also serve as the additive of jet fuel.
Traditional glycol monoethyl ether is made using methanol with reacting ethylene oxide, and oxirane obtains from petroleum path,
How to develop significant for solving petroleum resources anxiety situation from the process route of natural gas or coal base product.And
The process route from coal base route synthesis of oxalate and then Hydrogenation for glycol monoethyl ether that the present invention develops, is preferably solved
Resource problem.
In CN 103566949 glycol monoethyl ether is prepared using mesoporous zirconium dioxide material load copper-based catalysts
Method, the Zirconia carrier with soda acid both sexes cause catalyst of the present invention to obtain the high activity of high glycol monoethyl ether synthesis
And high selectivity；Due to the pore structure and high-ratio surface of mesoporous ZrO 2 rule so that the scattered effect that active specy is got well
Fruit, beneficial to the stability of catalyst.
The side for the silicon dioxide carried copper-molybdenum catalyst synthesizing glycol monomethyl ether developed in CN 103816915
Method, this method use amorphous or mesoporous silicon oxide as carrier, using metallic copper and metal molybdenum as active component, relatively warm
Under the hydroconversion condition of sum, high oxalic acid ester conversion rate and glycol monoethyl ether selectivity are obtained.
Catalyst research at present on hydrogenation of oxalate for preparing ethylene glycol monomethyl ether is few, uses copper mostly as active component
Catalyst carrier is typically chosen SiO2、ZrO2Deng oxide, catalytic mechanism is still not clear, and often sinters during the course of the reaction
Phenomenon and the inactivation for making catalyst, or even have influence on the industrialization process of whole technique.Therefore, prepared by dimethyl oxalate plus hydrogen second two
The life-span of alcohol monomethyl ether catalyst, activity, stability etc. need further to improve.
The content of the invention
The technical problems to be solved by the invention are that the glycol monoethyl ether being directed in conventional preparation techniques is selectively low, steady
The shortcomings that qualitative poor, there is provided a kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst, pass through sol-gal process
The copper-based catalysts that mesoporous silicon oxide load is made obtain glycol monoethyl ether catalyst through gel, aging, drying, roasting,
In the industrial production that can be widely used for glycol monoethyl ether.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst, step are as follows：
（1）Silicon source and organic solvent are mixed evenly, addition copper source continues to stir 0.5-5 hours, then adds molecular sieve
Additive continues to stir 0.5-5 hours；
（2）By step（1）In obtained solution under conditions of catalyst is not added, through gel, aging, drying, roasting, obtain institute
State catalyst.
One or more of the described silicon source in tetraethyl orthosilicate, methyl silicate or polysilicates.
One or more of the described copper source in copper nitrate, copper sulphate, copper acetate.
Described molecular sieve additive is at least one of ZSM-5 originals powder, MCM-22 originals powder, MCM-56 original powder.
Described organic solvent is at least one of methanol, ethanol, ethylene glycol.
The gelling temp is 70 DEG C -100 DEG C, aged at room temperature 12-24 hours.
The drying is that 12-24 hours are dried under conditions of 70 DEG C -110 DEG C.
The sintering temperature is 400-600 DEG C, roasting time 4-24h.
Obtained hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst, with mesoporous SiO2Or amorphous Si O2For carrier, with point
Son sieve is used as auxiliary agent, and using copper as main active component, by weight percentage, copper accounts for 5 ~ 45%, and auxiliary molecules sieve accounts for 0.01-5%,
Surplus is silica.
Described hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst prepares ethylene glycol list first for oxalate hydrogenation
Ether, step are as follows：Reaction is carried out in fixed bed reactors, will be put into fixed bed reactors after the shaping of catalyst prepared
In, use 5% H2/N2Being reduced, reduction temperature is 200-600 DEG C, hour recovery time 2-24, after reduction terminates, control
For temperature to 200-230 DEG C, methanol solution and the hydrogen reaction of pressure 2.0-3.0MPa, 10-25 wt% dimethyl oxalates generate second
Glycol, the mass space velocity of dimethyl oxalate is 0.5-2 h-1, hydrogen ester ratio is 60-200.
Experiment shows, catalyst of the invention has very high anti-in the reaction of preparing glycol through oxalate hydrogenation monomethyl ether
Should be active selective with glycol monoethyl ether, preparation technology is simple, active component high dispersive, long lifespan, reacting balance.
Beneficial effects of the present invention：Technical scheme employed in the present invention prepares ethylene glycol by using sol-gal process
Monomethyl ether catalyst, with mesoporous SiO2Or amorphous Si O2For carrier, auxiliary agent is used as by the use of molecular sieve so that both have on catalyst
There is metal catalytic center to include acid site again, esters hydrogenation and alcohols dehydration reaction can be completed on a catalyst, achieved good
Good catalytic effect；The technical scheme of catalyst of the present invention, efficiently solve the ethylene glycol list in conventional preparation techniques
The shortcomings that methyl ether is selectively low, stability is poor, this method carrier have preparation technology it is simple, it is good to active component dispersion effect,
The advantages that course of reaction moderate resistance caking power is strong, catalyst stability is high.This patent is used as using a small amount of mesopore molecular sieve to be added
Add agent, and non-carrier, avoiding the use of a large amount of molecular sieves causes being substantially increased for catalyst cost, on the other hand make use of again point
Son sieve is simpler to catalyst structure and the modulation of catalyst surface acid-base property, and in preparation technology in sol-gel process
It is single, achieve more excellent catalytic effect.
Embodiment
With reference to specific embodiment, the present invention will be further described.It should be understood that following examples are merely to illustrate this
Invention can make one not for limitation the scope of the present invention, the person skilled in the art in the field according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The preparation method step of the hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst of the present embodiment is as follows：
Weigh the water copper nitrates of 32.6 g five to be dissolved in 100 ml water, stirring is allowed to dissolve, and adds in the solution and prepares in advance
Tetraethyl orthosilicate ethanol solution 100ml, then add H-ZSM-5 original powder 0.5g and stir 4 hours, then heat to 90 DEG C
Gel, aged at room temperature 12 hours, 110 DEG C of dryings 12
Hour, 450 DEG C of roasting 12h obtain Cu/SiO2Catalyst.
Evaluating catalyst：Reaction is carried out in fixed bed reactors.The catalyst tabletting prepared is screened into 40-60
Mesh, the 1g that then weighs are put into reactor, use 5% H2/N2Middle reduction, overall flow rate are controlled in 100 ml/min, reduction temperature
250 DEG C, 10 hours recovery times.After reduction terminates, system is passed through with pure hydrogen, adjustment temperature is to 200 DEG C, control pressure
2.5MPa, hydrogen ester is than 80, dimethyl oxalate（DMO）Liquid quality air speed is 0.5 h-1, the first of raw material 20wt.% dimethyl oxalates
Alcoholic solution is fed with phase autoclave pump.It is separated by half an hour sampling to form with gas chromatographic analysis product, and DMO conversions is calculated
Rate and ethylene glycol（EG）Selectivity.It the results are shown in Table 1.
Embodiment 2
The preparation method step of the hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst of the present embodiment is as follows：
Weigh the water copper nitrates of 32.6 g five to be dissolved in 100 ml water, stirring is allowed to dissolve, and adds in the solution and prepares in advance
Polysilicates ethanol solution 150ml, then add H-ZSM-5 original powder 1g and stir 5 hours, then heat to 80 DEG C of gels,
Aged at room temperature 24 hours, 70 DEG C of dryings 24 hours, 600 DEG C of roastings obtain Cu/SiO in 4 hours2Catalyst.
Evaluating catalyst：Evaluating catalyst method the results are shown in Table 1 with embodiment 1.
Embodiment 3
The preparation method step of the hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst of the present embodiment is as follows：
Weigh the water copper nitrates of 15.1g five to be dissolved in 100 ml water, stirring is allowed to dissolve, and adds what is prepared in advance in the solution
Methyl silicate methanol solution 150ml, then add MCM-56 original powder 0.1g and stir 10 hours, then heat to 70 DEG C and coagulate
Glue, aged at room temperature 18 hours, 90 DEG C of dryings 15 hours, 400 DEG C are calcined 24 hours, obtain Cu/SiO2Catalyst is stand-by.
Evaluating catalyst：Evaluating catalyst method the results are shown in Table 1 with embodiment 1.
Embodiment 4
The preparation method step of the hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst of the present embodiment is as follows：
Weigh the water copper nitrates of 49.8g five to be dissolved in 200 ml water, stirring is allowed to dissolve, and adds what is prepared in advance in the solution
Tetraethyl orthosilicate ethylene glycol solution 100ml, then add MCM-22 original powder 0.5g and stir 4 hours, then heat to 100 DEG C and coagulate
Glue, aged at room temperature 12 hours, 110 DEG C of dryings 12 hours, 500 DEG C of roastings obtain Cu/SiO in 16 hours2Catalyst.
Evaluating catalyst：Evaluating catalyst method the results are shown in Table 1 with embodiment 1.
Embodiment 5
The preparation method step of the hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst of the present embodiment is as follows：
Weigh the water copper nitrates of 29.8g five to be dissolved in 100 ml water, stirring is allowed to dissolve, and adds what is prepared in advance in the solution
Tetraethyl orthosilicate ethylene glycol solution 100ml, it is small then to add H-ZSM-5 original powder 0.5g and MCM-56 original powder 0.5g stirrings 0.5
When, it is old to then heat to 100 DEG C of gels, room temperatures
Change 24 hours, 110 DEG C of drying 12 hours, 450 DEG C are calcined 12 hours and obtain Cu/SiO2Catalyst.
Evaluating catalyst：Evaluating catalyst method the results are shown in Table 1 with embodiment 1.
The evaluation result of the embodiment 1-5 catalyst of table 1
Embodiment 6
The preparation method of the hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst of the present embodiment is identical with embodiment 4, and what is obtained urges
Agent obtains Φ 5 × 4 cylinder shape catalyst using the method for beating sheetmolding.
Evaluating catalyst：Whole reaction is carried out on 300ml catalyst mode devices.300ml is weighed after beating sheetmolding
Catalyst be fitted into tubular fixed-bed reactor, use 5% H2/N2Reduction, H2Flow control in 20 ml/min, reduction
350 DEG C of temperature, 10 hours recovery times.After reduction terminates, system is passed through with pure hydrogen, adjustment temperature is to 200 DEG C, control pressure
2.5MPa, hydrogen ester is than 80, dimethyl oxalate（DMO）Liquid quality air speed is 0.5 h-1, the first of raw material 20wt.% dimethyl oxalates
Alcoholic solution is fed with phase autoclave pump.It is separated by half an hour sampling to form with gas chromatographic analysis product, and DMO conversions is calculated
Rate and glycol monoethyl ether selectivity.Stable reaction is run 200 hours activity and is not decreased obviously, and DMO conversion ratios are stable 98%
Left and right, glycol monoethyl ether yield reach more than 77%, and the catalyst shows splendid hydrogenation activity, glycol monoethyl ether choosing
Selecting property and life-span, show good application prospect.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
For art personnel it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification is explanation
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (10)
1. a kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst, it is characterised in that step is as follows：
（1）Silicon source and organic solvent are mixed evenly, addition copper source continues to stir, and then adds molecular sieve additive and continues
Stir 0.5-10 hours；
（2）By step（1）In obtained solution under conditions of catalyst is not added, through gel, aging, drying, roasting, obtain institute
State catalyst.
2. the preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst according to claim 1, it is characterised in that：
One or more of the described silicon source in tetraethyl orthosilicate, methyl silicate or polysilicates.
3. the preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst according to claim 1, it is characterised in that：
One or more of the described copper source in copper nitrate, copper sulphate, copper acetate.
4. the preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst according to claim 1, it is characterised in that：
Described molecular sieve additive is at least one of ZSM-5 originals powder, MCM-22 originals powder, MCM-56 original powder.
5. the preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst according to claim 1, it is characterised in that：
Described organic solvent is at least one of methanol, ethanol, ethylene glycol.
6. the preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst according to claim 1, it is characterised in that：
The gelling temp is 70 DEG C -100 DEG C, aged at room temperature 12-24 hours.
7. the preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst according to claim 1, it is characterised in that：
The drying is that 12-24 hours are dried under conditions of 70 DEG C -110 DEG C.
8. the preparation method of hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst according to claim 1, it is characterised in that：
The sintering temperature is 400-600 DEG C, roasting time 4-24h.
9. according to hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst made from any described preparation method of claim 1 ~ 8,
With mesoporous SiO2Or amorphous Si O2For carrier, using molecular sieve as auxiliary agent, using copper as main active component, with percentage by weight
Meter, copper account for 5 ~ 45%, and auxiliary molecules sieve accounts for 0.01-5%, and surplus is silica.
10. hydrogenation of oxalate for preparing ethylene glycol monomethyl ether catalyst according to claim 9 is used for oxalate hydrogenation system
Standby glycol monoethyl ether, it is characterised in that step is as follows：Reaction carried out in fixed bed reactors, by the catalyst prepared into
It is put into after type in fixed bed reactors, uses 5% H2/N2Reduced, reduction temperature is 200-600 DEG C, recovery time 2-24
Hour, after reduction terminates, control temperature is to 200-230 DEG C, the methanol of pressure 2.0-3.0MPa, 10-25 wt% dimethyl oxalates
Solution and hydrogen reaction generation ethylene glycol, the mass space velocity of dimethyl oxalate is 0.5-2 h-1, hydrogen ester ratio is 60-200.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585890A (en) * | 1981-04-30 | 1986-04-29 | Ube Industries, Ltd. | Process for producing ethylene glycol and/or glycolic acid ester, catalyst composition used therefor, and process for production thereof |
| CN102091650A (en) * | 2011-01-18 | 2011-06-15 | 厦门大学 | Oxalic ester hydrogenated copper silicon catalyst and preparation method thereof |
| CN103566949A (en) * | 2013-11-05 | 2014-02-12 | 复旦大学 | Copper-based catalyst for preparing ethylene glycol and ethylene glycol monomethyl ether through hydrogenation of dimethyl oxalate and preparation method thereof |
| CN103816915A (en) * | 2014-02-25 | 2014-05-28 | 神华集团有限责任公司 | Catalyst for preparing ethylene glycol monomethyl ether by hydrogenation of dimethyl oxalate and methanol and process thereof |
-
2017
- 2017-09-19 CN CN201710845632.1A patent/CN107537552A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585890A (en) * | 1981-04-30 | 1986-04-29 | Ube Industries, Ltd. | Process for producing ethylene glycol and/or glycolic acid ester, catalyst composition used therefor, and process for production thereof |
| CN102091650A (en) * | 2011-01-18 | 2011-06-15 | 厦门大学 | Oxalic ester hydrogenated copper silicon catalyst and preparation method thereof |
| CN103566949A (en) * | 2013-11-05 | 2014-02-12 | 复旦大学 | Copper-based catalyst for preparing ethylene glycol and ethylene glycol monomethyl ether through hydrogenation of dimethyl oxalate and preparation method thereof |
| CN103816915A (en) * | 2014-02-25 | 2014-05-28 | 神华集团有限责任公司 | Catalyst for preparing ethylene glycol monomethyl ether by hydrogenation of dimethyl oxalate and methanol and process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张德祥编著: "《煤制油技术基础与应用研究》", 31 January 2013 * |
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