CN101524646A - Glycol catalyst synthesized by hydrogenating oxalic ester and preparation method and application thereof - Google Patents
Glycol catalyst synthesized by hydrogenating oxalic ester and preparation method and application thereof Download PDFInfo
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- CN101524646A CN101524646A CN200910030878A CN200910030878A CN101524646A CN 101524646 A CN101524646 A CN 101524646A CN 200910030878 A CN200910030878 A CN 200910030878A CN 200910030878 A CN200910030878 A CN 200910030878A CN 101524646 A CN101524646 A CN 101524646A
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- catalyst
- ethylene glycol
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- oxalic ester
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Abstract
The invention discloses a glycol catalyst synthesized by hydrogenating oxalic ester and a preparation method and an application thereof. The catalyst has the chemical formula of CuO-AOx/Al2O3, wherein A is one or more than one metallic element of Zn, Mn, Mg and Cr, x is half of the valence number of A, the content of CuO accounts for 40 percent to 80 percent of the catalyst mass, the content of AOx accounts for 5 percent to 40 percent of the catalyst mass and the content of Al2O3 accounts for 5 percent to 30 percent of the catalyst mass. The catalyst has high activity and selectivity at low temperature and under low pressure, the energy and power consumption in production can be reduced greatly and the catalyst has good stability and long service life. The preparation method of the catalyst is simple and raw materials as industrial products are easily obtained and have low price.
Description
Technical field
The invention belongs to the catalyst chemical field, particularly a kind of oxalic ester hydrogenation synthesizing of ethylene glycol Catalysts and its preparation method and application.
Background technology
Ethylene glycol is important Organic Chemicals, be mainly used in and produce polyester fiber, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, non-ionic surface active agent and explosive etc., can be used for coating in addition, industry such as the developer solution of taking pictures, brake-fluid and printing ink, solvent and medium as ammonium pertorate, be used to produce special solvent glycol ether etc., purposes is very extensive.
The industrial production of China's ethylene glycol starts from the sixties in 20th century, and what adopt at the beginning is traditional chlorethanol Hydrolyze method, promptly utilizes chlorethanol and alkali reaction to generate oxirane, makes ethylene glycol by the oxirane hydrolysis again.The method energy consumption is big, and product purity is poor, and the production cost height is seriously polluted, backward in technique, is not suitable for large-scale production.Since seventies oil crisis, countries in the world are dropped into lot of manpower and material resources oil substitutes are developed, and are the C of raw material with low-cost resources such as coal, natural gases wherein
1Chemical research is the most active.Development C
1Chemical industry not only can make full use of natural gas and coal resource, and can alleviate environmental pressure, is unusual important field of research.Ube Industries Ltd. eighties is the technology of back end hydrogenation preparing ethylene glycol with regard to having developed the CO synthesis of oxalate, and obtained major progress.The coal resource of China is abundant relatively, and exploitation is that the technology of the oxalate method synthesizing glycol of raw material has crucial meaning with CO, can effectively alleviate the degree of dependence of China to oil.
Oxalate method synthesizing glycol is divided into CO oxidative coupling synthesis of oxalate and two steps of oxalate catalytic hydrogenation preparing ethylene glycol.Wherein oxalate catalytic hydrogenation preparing ethylene glycol is to realize industrialized key.Since the eighties, the patent of a series of hydrogenation of oxalate for preparing ethylene glycol catalyst has been applied in countries in the world, its shortcoming is catalyst reaction temperatures height, pressure height, heat and power consumption are big, the conversion ratio and the selectivity of reaction are not very desirable, be not suitable for suitability for industrialized production, and catalyst are not easy to separate with product, space-time yield is not high, and catalyst is short service life.
Summary of the invention
The present invention aims to provide a kind of oxalic ester hydrogenation synthesizing of ethylene glycol Catalysts and its preparation method and application that helps suitability for industrialized production, this catalyst promptly has high activity and high selectivity under low-temp low-pressure, can significantly reduce the energy and the power consumption of production, and good stability, long service life.This Preparation of catalysts method is simple, and raw material sources are easy to get, and are technical grade product, and are cheap.
The present invention is achieved by the following technical programs.
A kind of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, its chemical formula are CuO-AO
x/ Al
2O
3, described A is one or more in Zn, Mn, Mg, the Cr metallic element, and x is 1/2 of an A valence mumber, and CuO content is 40%～80% of catalyst quality, AO
xContent is 5%～40% of catalyst quality, Al
2O
3Content is 5%～30% of catalyst quality.
Above-mentioned a kind of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, wherein, described specific surface area of catalyst is 80～500m
2/ g, pore volume are 0.2～1.2cm
3/ g, average pore radius is 2～20nm.
A kind of oxalic ester hydrogenation synthesizing of ethylene glycol Preparation of catalysts method, wherein, comprise the steps: mixed solution and precipitant mix reaction with slaine, reaction end pH value is 7～8, reacting rear material finally makes the target catalyst through bubbling, washing, filtration, drying, grinding, roasting, moulding.
Above-mentioned a kind of oxalic ester hydrogenation synthesizing of ethylene glycol Preparation of catalysts method, wherein, described precipitating reagent is a urea.
Above-mentioned a kind of oxalic ester hydrogenation synthesizing of ethylene glycol Preparation of catalysts method, wherein, described baking temperature is 90～100 ℃, be 10～16 hours drying time; Sintering temperature is 350～600 ℃, and roasting time is 2～4 hours.
A kind of oxalic ester hydrogenation synthesizing of ethylene glycol Application of Catalyst, reaction pressure is 0.3～1.0MPa, and reaction temperature is 145～220 ℃, and the oxalate liquid hourly space velocity (LHSV) is 0.1～0.6g/g (cat) .h, oxalate is converted into the conversion ratio of glycol reaction greater than 99%, and the selectivity of ethylene glycol is greater than 90%.
The reaction equation of oxalic ester hydrogenation synthesizing of ethylene glycol is as follows:
CH
3OOCCOOCH
3+2H
2→CH
3OOCCH
2OH+CH
3OH
CH
3OOCCH
2OH+2H
2→HOCH
2CH
2OH+CH
3OH
Reaction also generates kind of accessory substance surplus dimethyl carbonate, ethanol, propane diols, butanediol and the gamma-butyrolacton etc. 50 except that generating ethylene glycol and methyl alcohol, return the oxalate synthesizing section behind the methanol rectification that generates in the reaction and recycle.
Catalyst of the present invention is compared with existing catalyst has following characteristics:
(1) reaction pressure and reaction temperature are low, and catalyst of the present invention just has hydrogenation activity preferably when 0.3MPa, and this pressure generally is lower than other patent 1.0～1.5MPa; In the time of 145 ℃, just has high reaction activity and high, this reaction temperature generally is lower than 25～50 ℃ of other patents, under so low reaction pressure and temperature conditions, will greatly reduce the cost of investment of permanent plant, reduced energy consumption, extremely beneficial to suitability for industrialized production.
(2) this catalyst stability is good, and the life-span is long, and is active high, the conversion ratio of oxalate 〉=99%, the selectivity of ethylene glycol 〉=90%.Catalyst of the present invention turned round for a long time through 5000 hours, stable reaction, and do not have obvious deactivation phenomenom.
(3) raw material sources of catalyst are easy to get, and are technical grade product, and are cheap, reduced production cost.
(4) adopt catalyst of the present invention make in the byproduct of reaction heavy ends seldom, target product is easy to separate, degree of purity of production reaches 99.5%.
The specific embodiment
The invention will be further described by the following examples:
A kind of oxalic ester hydrogenation synthesizing of ethylene glycol Catalysts Cu O-AO
x/ Al
2O
3, A is one or more in Zn, Mn, Mg, the Cr metallic element, CuO content is 40%～80% of catalyst quality, AO
xContent is 5%～40% of catalyst quality, Al
2O
3Content is 5%～30% of catalyst quality.
Preparation of Catalyst: with precipitating reagent and distilled water mixed dissolution, metal salt solution is mixed the back to add in the above-mentioned precipitant solution, stirring and evenly mixing, be warming up to 90～95 ℃ of stirrings 18～24 hours that reflux, the control endpoint pH is 7～8, and reaction finishes to stir bubbling again 2 hours, catalyst through washing, filter after 90～100 ℃ of dryings 10～16 hours, again catalyst is ground the back 350～600 ℃ of following roastings 2～4 hours, at last with the molded target catalyst that makes of tablet press machine.
Catalyst is used: the target catalyst is placed fixed bed reactors, with catalyst at 220～280 ℃, reductase 12 under the hydrogen gas stream～10 hour, hydrogen gas space velocity 3000～8000h
-1With after the oxalate heating for dissolving by metering piston pump with enter fixed bed reactors after hydrogen mixes, reaction process condition is: 145～220 ℃ of temperature, reaction pressure 0.3～1.0MPa, the oxalate liquid hourly space velocity (LHSV) is 0.1～0.6g/g (cat) .h, hydrogen gas space velocity 2400～4500h
-1
Embodiment 1
97g urea is poured in the there-necked flask, added 2000g distilled water, stirring makes it to dissolve fully, with 121.5g Cu (NO
3)
2.3H
2O, 146.2g Zn (NO
3)
2.6H
2O and 147g Al (NO
3)
3.9H
2O places beaker, adds 1500g distilled water it is dissolved fully.The mixed salt solution of preparation is joined in the urea liquid, and stirring is warming up to 95 ℃, back flow reaction control endpoint pH is 7.2, bubbling 2 hours again after reaction finishes, catalyst through washing, filter after 90 ℃ of dryings 10 hours, it is worn into fine powder,, form the particle of 3 * 5mm again through compressing tablet 350 ℃ of following roastings 2 hours.The specific surface area of catalyst of above-mentioned preparation is 80m
2/ g, pore volume are 0.3cm
3/ g, average pore radius is 3nm.
Catalyst is used: the catalyst that makes more than inciting somebody to action places fixed bed reactors, progressively is warming up to 220 ℃ with 10 ℃/h under pure hydrogen, and reduces 3 hours down at 220 ℃, and hydrogen gas space velocity is controlled at 3000h
-1With after the oxalate heating for dissolving by metering piston pump with enter fixed bed reactors after hydrogen mixes, reaction process condition and reaction result see Table 1.
Embodiment 2
130g urea is poured in the there-necked flask, added 2000g distilled water, stirring makes it to dissolve fully, with 190.2g Cu (NO
3)
2.3H
2O, 94.7g Cr (NO
3)
2.9H
2O, 9.2g Mn (NO
3)
3.9H
2O and 220.6gAl (NO
3)
3.9H
2O places beaker, adds 2000g distilled water it is dissolved fully.The mixed salt solution of preparation is joined in the urea liquid, and stirring is warming up to 93 ℃, back flow reaction control endpoint pH is 7.6, reaction finished bubbling 2 hours again, catalyst through washing, filter after 95 ℃ of dryings 14 hours, it is worn into fine powder,, form the particle of 3 * 5mm again through compressing tablet 500 ℃ of following roastings 2 hours.The specific surface area of catalyst of above-mentioned preparation is 450m
2/ g, pore volume are 1.1cm
3/ g, average pore radius is 10nm.Catalyst is used: the catalyst that makes more than inciting somebody to action places fixed bed reactors, progressively is warming up to 240 ℃ with 10 ℃/h under pure hydrogen, and reduces 5 hours down at 240 ℃, and hydrogen gas space velocity is controlled at 4000h
-1With after the oxalate heating for dissolving by metering piston pump with enter fixed bed reactors after hydrogen mixes, reaction process condition and reaction result see Table 1.
Embodiment 3
86g urea is poured in the there-necked flask, added 2000g distilled water, stirring makes it to dissolve fully, with 220gCu (NO
3)
2.3H
2O, 36.6g Zn (NO
3)
2.6H
2O, 31.8g Mg (NO
3)
2.6H
2O and 36.8g Al (NO
3)
3.9H
2O places beaker, adds 1500g distilled water it is dissolved fully.The mixed salt solution of preparation is joined in the urea liquid, and stirring is warming up to 90 ℃, back flow reaction control endpoint pH is 8.0, bubbling 2 hours again after reaction finishes, catalyst through washing, filter after 100 ℃ of dryings 16 hours, it is worn into fine powder,, form the particle of 3 * 5mm again through compressing tablet 600 ℃ of following roastings 3 hours.The specific surface area of catalyst of above-mentioned preparation is 150m
2/ g, pore volume are 0.6cm
3/ g, average pore radius is 15nm.
Catalyst is used: the catalyst that makes more than inciting somebody to action places fixed bed reactors, progressively is warming up to 260 ℃ with 10 ℃/h under pure hydrogen, and reduces 6 hours down at 260 ℃, and hydrogen gas space velocity is controlled at 7000h
-1With after the oxalate heating for dissolving by metering piston pump with enter fixed bed reactors after hydrogen mixes, reaction process condition and reaction result see Table 1.
Embodiment 4
With 62g urea and 31g Al (OH)
3Pour in the there-necked flask, add 2000g distilled water, stir and make it mixing, 121.5g Cu (NO
3)
2.3H
2O and 146.2g Zn (NO
3)
2.6H
2O places and burns the bosom, adds 1500g distilled water it is dissolved fully.The mixed salt solution of preparation is joined urea and Al (OH)
3Mixed solution in, and stir and to be warming up to 95 ℃, back flow reaction control endpoint pH is 7.5, bubbling 2 hours again after reaction finishes, catalyst through washing, filter after 90 ℃ of dryings 12 hours, it is worn into fine powder, 400 ℃ of following roastings 4 hours, form the particle of 3 * 5mm again through compressing tablet.The specific surface area of catalyst of above-mentioned preparation is 310m
2/ g, pore volume are 0.8cm
3/ g, average pore radius is 18nm.
Catalyst is used: the catalyst that makes more than inciting somebody to action places fixed bed reactors, progressively is warming up to 220 ℃ with 10 ℃/h under pure hydrogen, and reduces 4 hours down at 220 ℃, and hydrogen gas space velocity is controlled at 6000h
-1With after the oxalate heating for dissolving by metering piston pump with enter fixed bed reactors after hydrogen mixes, reaction process condition and reaction result see Table 1.
Table 1 evaluating catalyst data
| Embodiment | Reaction pressure (MPa) | Reaction temperature (℃) | Hydrogen gas space velocity (h -1) | Oxalate liquid hourly space velocity (LHSV) g/g (cat) h | Conversion ratio (%) | Selectivity (%) |
| 1 | 0.3 | 150 | 2500 | 0.2 | 99.6 | 96 |
| 2 | 1.0 | 220 | 4000 | 0.6 | 99.2 | 91 |
| 3 | 0.8 | 190 | 3000 | 0.3 | 99.7 | 94 |
| 4 | 0.5 | 200 | 4500 | 0.4 | 99.5 | 92 |
Claims (6)
1, a kind of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst is characterized in that, its chemical formula is CuO-AO
x/ Al
2O
3, described A is one or more in Zn, Mn, Mg, the Cr metallic element, and x is 1/2 of an A valence mumber, and CuO content is 40%～80% of catalyst quality, AO
xContent is 5%～40% of catalyst quality, Al
2O
3Content is 5%～30% of catalyst quality.
2, a kind of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst as claimed in claim 1 is characterized in that, described specific surface area of catalyst is 80～500m
2/ g, pore volume are 0.2～1.2cm
3/ g, average pore radius is 2～20nm.
3, a kind of oxalic ester hydrogenation synthesizing of ethylene glycol Preparation of catalysts method as claimed in claim 1, it is characterized in that, comprise the steps: mixed solution and precipitant mix reaction with slaine, reaction end pH value is 7～8, reacting rear material finally makes the target catalyst through bubbling, washing, filtration, drying, grinding, roasting, moulding.
4, a kind of oxalic ester hydrogenation synthesizing of ethylene glycol Preparation of catalysts method as claimed in claim 3 is characterized in that described precipitating reagent is a urea.
5, a kind of oxalic ester hydrogenation synthesizing of ethylene glycol Preparation of catalysts method as claimed in claim 3 is characterized in that described baking temperature is 90～100 ℃, and be 10～16 hours drying time; Sintering temperature is 350～600 ℃, and roasting time is 2～4 hours.
6, a kind of oxalic ester hydrogenation synthesizing of ethylene glycol Application of Catalyst, it is characterized in that, reaction pressure is 0.3～1.0MPa, reaction temperature is 145～220 ℃, the oxalate liquid hourly space velocity (LHSV) is 0.1～0.6g/g (cat) .h, oxalate is converted into the conversion ratio of glycol reaction greater than 99%, and the selectivity of ethylene glycol is greater than 90%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934228A (en) * | 2010-09-30 | 2011-01-05 | 江苏丹化煤制化学品工程技术有限公司 | Catalyst for preparing alcohol by acetic ester hydrogenation as well as preparation method and application thereof |
| WO2011160577A1 (en) | 2010-06-24 | 2011-12-29 | 天津大学 | Catalyst having monolithic structure for manufacturing ethylene glycol by oxalate hydrogenation, preparation method and application thereof |
| CN101700496B (en) * | 2009-10-21 | 2012-03-07 | 江苏丹化醋酐有限公司 | Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof |
| CN102380391A (en) * | 2010-08-26 | 2012-03-21 | 中科合成油技术有限公司 | Selective deacidification catalyst, preparation method thereof and application thereof to selective hydrogenation deacidification treatment of Fisher-Tropsch synthetic oil |
| CN102649690A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for improving selectivity of ethylene glycol prepared through hydrogenation reaction by oxalic ester |
| CN102731335A (en) * | 2012-06-25 | 2012-10-17 | 江苏丹化煤制化学品工程技术有限公司 | Post-processing method of oxalate ester hydrogenation reaction solution |
| CN104785261A (en) * | 2015-03-19 | 2015-07-22 | 河南能源化工集团研究院有限公司 | Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof |
| CN105435799A (en) * | 2015-11-09 | 2016-03-30 | 华东理工大学 | Catalyst for ethanol preparation by ethyl acetate hydrogenation and preparation method for catalyst |
| CN109569618A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of catalyst for acetate low temperature hydrogenation and preparation method thereof and acetic acid ester through hydrogenation alcohol |
-
2009
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101700496B (en) * | 2009-10-21 | 2012-03-07 | 江苏丹化醋酐有限公司 | Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof |
| WO2011160577A1 (en) | 2010-06-24 | 2011-12-29 | 天津大学 | Catalyst having monolithic structure for manufacturing ethylene glycol by oxalate hydrogenation, preparation method and application thereof |
| CN102380391A (en) * | 2010-08-26 | 2012-03-21 | 中科合成油技术有限公司 | Selective deacidification catalyst, preparation method thereof and application thereof to selective hydrogenation deacidification treatment of Fisher-Tropsch synthetic oil |
| CN101934228A (en) * | 2010-09-30 | 2011-01-05 | 江苏丹化煤制化学品工程技术有限公司 | Catalyst for preparing alcohol by acetic ester hydrogenation as well as preparation method and application thereof |
| CN102649690A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for improving selectivity of ethylene glycol prepared through hydrogenation reaction by oxalic ester |
| CN102731335A (en) * | 2012-06-25 | 2012-10-17 | 江苏丹化煤制化学品工程技术有限公司 | Post-processing method of oxalate ester hydrogenation reaction solution |
| CN102731335B (en) * | 2012-06-25 | 2015-12-09 | 江苏丹化煤制化学品工程技术有限公司 | A kind of post-treating method of oxalate hydrogenation liquid |
| CN104785261A (en) * | 2015-03-19 | 2015-07-22 | 河南能源化工集团研究院有限公司 | Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof |
| CN105435799A (en) * | 2015-11-09 | 2016-03-30 | 华东理工大学 | Catalyst for ethanol preparation by ethyl acetate hydrogenation and preparation method for catalyst |
| CN109569618A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of catalyst for acetate low temperature hydrogenation and preparation method thereof and acetic acid ester through hydrogenation alcohol |
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Application publication date: 20090909 |