CN101733108A - Catalyst for hydrogenation, preparation method thereof and use thereof - Google Patents
Catalyst for hydrogenation, preparation method thereof and use thereof Download PDFInfo
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- CN101733108A CN101733108A CN200810203505A CN200810203505A CN101733108A CN 101733108 A CN101733108 A CN 101733108A CN 200810203505 A CN200810203505 A CN 200810203505A CN 200810203505 A CN200810203505 A CN 200810203505A CN 101733108 A CN101733108 A CN 101733108A
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Abstract
The invention provides a catalyst for hydrogenation, a preparation method thereof and use thereof. The chemical formula of the catalyst is CuOx-ROy/SiO2. The catalyst of the invention is used for hydrogenation in a gas-phase method for preparing glycol and is prepared from the raw materials including but not limited to oxalate or ethyl glycolate and hydrogen. The catalyst of the invention requires low reaction temperature and allows for a wide temperature range. The catalyst of the invention has extremely high operation elasticity, high activity and selectivity within a temperature range of 160 to 260 DEG C and a pressure range of 1 to 10 MPa, high time space yield, over 99 percent raw material conversion rate, over 96 percent target product selectivity, less than 0.1 percent by-product yield, high stability and a one-pass service life of up to 3,500 hours. The catalyst can greatly reduce energy consumption, save follow-up product separation equipment and procedures reduce production cost and avoid equipment corrosion and environmental pollution.
Description
Technical field
The present invention relates to a kind of catalyst for hydrogenation and its production and application.
Background technology
Polyalcohol is a kind of important Organic Chemicals, wherein as ethylene glycol, be mainly used in and make non-ionic surface active agent, monoethanolamine, polyester fiber, antifreezing agent and explosive etc., also be used to prepare low-freezing cooling fluid (engine is used), also can directly be used as solvent.In addition, in tobacco industry, textile industry and cosmetic industry extensive use is arranged also.
The most of petroleum path that adopts of the existing production technology of ethylene glycol is a raw material with ethene, and first direct oxidation method is produced oxirane, makes ethylene glycol through liquid-phase catalysis or on-catalytic hydration again.All this route is disclosed as Chinese patent 02112038.2, United States Patent (USP) 5874653, Japan Patent 82106631.This method is discharged a large amount of waste water in process of production, the product separation difficulty, the energy consumption height, pollute high, cost is high.
At the end of the seventies in last century, L R Jehner etc. at first proposes the technology path of oxalate gas phase hydrogenation preparing ethylene glycol in Japan Patent 5323011,5542971; Haruhiko Miyazaki in 1985 etc. disclose CuMo in United States Patent (USP) 4551565
kBa
pO
xCatalyst, than being diethy-aceto oxalate all can be transformed under 200 the condition, glycol selectivity is 97.7% to this catalyst at 0.1MPa, 177 ℃, hydrogen ester, and the shortcoming of this catalyst is that the reaction hydrogen ester is higher, liquid hourly space velocity (LHSV) lower (about 0.036g/g cat.h), catalyst life does not appear in the newspapers.
To produce the higher alcohols accessory substance in the preparing glycol by hydrogenating oxalate process, even such accessory substance content very low (0.1%wt) also can have a strong impact on product quality, and separation difficulty, energy consumption is big, reported a kind of catalyst in the European patent 0060787, it can control this accessory substance under the situation of accurately controlling reaction condition, and its mass fraction in product is about 1%, but its shortcoming is Cr element and the controlled condition harshness that needs to add severe toxicity in its catalyst, is difficult to industrialization.
U.S. ARCO company in 1986 adopts the Cu-Cr catalyst, and under loaded catalyst 100mL, 3.0MPa pressure, the ethylene glycol yield is 95%, the long running 466h of catalyst.
Chinese Academy of Sciences's Fujian thing structure finish the 200mL mould examination research work of diethy-aceto oxalate hydrogenation preparing ethylene glycol in the early 1990s.They use the Ec-13 Cu-Cr catalyst, under 0.6MPa~3.0MPa, 205 ℃~240 ℃, liquid hourly space velocity (LHSV) 0.327g/g cat.h condition, and running 1134h, space-time yield 142g/lh.Above catalyst is short service life, and the oxalate gas phase hydrogenation prepares ethylene glycol technology does not have the industrial applications precedent at present.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst for hydrogenation and its production and application, to overcome the above-mentioned defective that prior art exists.
Catalyst for hydrogenation of the present invention, its chemical formula is:
CuOx-ROy/SiO
2
Wherein: SiO
2Be carrier;
R is selected from one or more in alkali earth metal, transition metal or the thulium:
X is 1/2 of a Cu valence mumber;
Y is 1/2 of a R valence mumber;
In total catalyst weight is 100 parts, and the content of R element is 0~15 part, and the content of Cu element is 10~70 parts;
Preferably, be 100 parts in described total catalyst weight, the content of R element is 0.01~10 part, the content of Cu element is 15~60 parts;
Total catalyst weight refers to CuOx-ROy and SiO
2The gross weight of carrier;
Preferably, described R is selected from one or more among Ca, Ba, Mn, Mo, Co, Zr, Zn, Pd, Ru, Pt, La, Eu or the Ce;
Preferably, described SiO
2For specific surface at 5m
2/ g~1000m
2In/g the scope is the setting or the amorphous materials of agent structure with Si-O, derives from silica gel, diatomite, white carbon, estersil or the Ludox one or more;
The preparation method of above-mentioned catalyst for hydrogenation in turn includes the following steps:
(1) with silicon source, water and Cu salting liquid or silicon source, Cu salting liquid and R salt solution mix, add acidity or alkaline matter, regulating the pH value is 1~6, add precipitant solution then, reacted under proper condition 0.5~48 hour, preferred 10~30 hours, control reaction solution endpoint pH was 7~14, preferred 8~12, the solid matter in the collecting reaction product;
Described Cu salt or R salt are selected from one or more in the water-soluble salt such as nitrate, acetate or halide;
Described precipitating reagent is alkaline precipitating agent or the preformed precipitate agent that can generate alkaline matter under certain condition, includes but not limited to carbonate, ammoniacal liquor or urea etc.;
Described acidity or alkaline matter are selected from but are not limited to inorganic acid alkali, organic acids and base or some salt.
The reaction of described felicity condition includes but not limited to stir, aging, condensing reflux etc.
The weight portion consumption of each component is:
SiO
2Weight portion be 1~85, preferred 20~60 weight portions, the weight portion of water are 200 parts, the weight portion of precipitating reagent is 1~100, preferred 40~80 weight portions, the weight portion of Cu element are 10~70, the weight portion of R element is 0~15;
(2) solid matter that step (1) is collected through washing after, at 80~200 ℃, preferred 90-120 ℃ dry 4~24 hours down, preferred 10~16 hours;
(3) with the product of step (2) at 300~600 ℃, preferred 400~500 ℃ of following roastings are more than 0.5 hour, and are preferred 2~6, calcination atmosphere can carry out in air, nitrogen, carbon dioxide or ammonia atmosphere, obtains described catalyst.
Catalyst of the present invention can be used for oxalate or the ethyl glycolate hydrogenation reaction prepares ethylene glycol, and application process comprises the steps:
(1) described catalyst was reduced 4~20 hours under 200~500 ℃, hydrogen atmosphere, hydrogen volume concentration is 0.5%~100%;
(2) be dissolved in the solvent with oxalate or ethyl glycolate heat fused or with it, contact with hydrogen in the presence of described catalyst then, the liquid hourly space velocity (LHSV) of oxalate or ethyl glycolate is 0.01~5.4g/g cat.h, and the hydrogen ester ratio is 20~500; Reaction temperature is 160~260 ℃, and reaction pressure is 1~10MPa.
Described solvent is including, but not limited to alcohols, ester class etc., and the weight content of oxalate or ethyl glycolate is 1~60%.
Adopt catalyst of the present invention, when being used to prepare the vapor phase method hydrogenation reaction of ethylene glycol, its raw material includes but not limited to oxalate or ethyl glycolate and hydrogen.Similarly, according to those of ordinary skills' general knowledge, this catalyst also can apply to prepare the hydrogenation preparing reaction of other polyalcohols such as glycerine analogically.This catalyst does not have the selectivity requirement to the raw material of preparation polyalcohol.
Catalyst of the present invention is compared with existing catalyst has following characteristics:
Reaction temperature is low, and temperature range is wide.Catalyst of the present invention has splendid operating flexibility, at 160-260 ℃, all have higher activity and selectivity in 1~10MPa scope, space-time yield height, feed stock conversion are more than 99%, target product selectivity is more than 96%, the impurity content that accessory substance especially has a strong impact on the target product performance is lower than 0.1%, and catalyst stability is good, and the life-span is long, the one way life-span reaches 3500 hours, reaches the industrial applications standard substantially.Adopt catalyst of the present invention can significantly reduce heat and power consumption, reduce subsequent product separation equipment and operation, reduce production costs.Relatively document is lower for technology hydrogen ester of the present invention, greatly reduces costs such as energy consumption and separation.Catalyst of the present invention does not have corrosion to equipment, environmentally safe.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, as the catalyst chemical operation manual, or the condition of advising according to manufacturer.
Embodiment 1
The first step is poured treated 45g white carbon in the round-bottomed flask into, and mixing and add the nitre acid for adjusting pH value with the 100g deionized water is 3.360g is contained 118g Cu (NO
3)
2Copper nitrate solution mix mutually with above-mentioned solution, mix be placed in 75 ℃ of water-baths standby;
Second ammonia spirit that goes on foot the 5wt% that will prepare slowly is added drop-wise in the above-mentioned solution, keeps stirring, water-bath to reflux in the dropping process; Control terminal point pH value of solution value is 8.
After filtering feed liquid while hot, the three-step reaction end, washs also suction filtration of back through ethanol again through the washing of several deionized water;
The 4th step catalyst filter cake through 95 ℃ of dryings after 12 hours 450 ℃ of following roastings 6 hours.Obtain catalyst, code name is A.
The broken screening of catalyst A 40-60 order is placed reaction tube; Reaction tube is risen to 200 ℃ from room temperature with 2 ℃/min speed, and therebetween, hydrogen content increases to 100% gradually from 0.5%, and finally is adjusted to reaction process condition in reduction under the pure hydrogen after 6 hours and reacts.Reaction raw materials is selected diethy-aceto oxalate.
Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 2
The first step is poured 40g diatomite in the round-bottomed flask into, mixes the back with the 200g deionized water and adds the 60g potash solid, mix be placed in 75 ℃ of water-baths standby; The pH value is 12;
Second step preparation 200g contains 88g Cu (NO
3)
2With 3g Ni (NO
3)
2Copper nitrate/nickel nitrate solution.
The 3rd step slowly was added drop-wise to this metallic solution in the diatomite mixed solution, and electronic stirring and 75 ℃ of water-bath back flow reaction left standstill after 2 hours 8 hours, and control pH value is 9; Carry out the post-processing operation such as washing and drying of catalyst with reference to embodiment 1, catalyst, code name is B.
The broken screening of catalyst B 20-40 order is placed reaction tube; Reaction tube is risen to 350 ℃ from room temperature with 4 ℃/min speed, and therebetween, hydrogen content increases to 100% gradually from 0.5%, and finally is adjusted to reaction process condition in reduction under the pure hydrogen after 4 hours and reacts.Reaction raw materials is selected dimethyl oxalate.
Catalyst reaction process conditions and the results are shown in Table 1.This catalyst has been finished the 3500h stability experiment under this condition.
Embodiment 3
Preparation of Catalyst is with embodiment 2, and difference is second step was replaced by 88g Gu (NO
3)
2, 1.5gCo (NO
3)
2With 1.5g Mn (NO
3)
2Mixed solution.Get catalyst, code name C.
Reducing condition is for to rise to 300 ℃ from room temperature with 2 ℃/min speed with reaction tube, and therebetween, hydrogen content increases to 100% gradually from 10%, and finally is adjusted to reaction process condition in reduction under the pure hydrogen after 6 hours and reacts.
Reaction raw materials is a methyl glycollate, catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 4
First step preparation 150 contains 88g Cu (NO
3)
2With 3g Zr (NO
3)
2Copper nitrate/zirconium nitrate solution.
Second step, above-mentioned solution incipient impregnation was in 150g silica gel.
Carry out the post-processing operation such as washing and drying of catalyst with reference to embodiment 1.Get catalyst, code name D.
Reaction raw materials is a dimethyl oxalate, catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 5
The first step is poured the 40g white carbon in the round-bottomed flask into, and diluting and add the nitre acid for adjusting pH value with the 200g deionized water is 3.
Second step, the 2g nickel nitrate mixed mutually with above-mentioned solution with 100g copper nitrate solid, and adding 80g urea also stirs.Stirring and dissolving is placed under 95 ℃ of water-baths and refluxed 20 hours, and control final solution pH value is 8.
Carry out the post-processing operation such as washing and drying of catalyst with reference to embodiment 1.Get catalyst, code name E.
Reaction raw materials is selected diethy-aceto oxalate.Catalyst reaction process conditions and the results are shown in Table 1.
The contrast of table 1 catalyst examination data
Catalyst | Reaction temperature/℃ | Reaction pressure/MPa | The hydrogen ester ratio | Material liquid hourly space velocity/g/g cat.H | Feed stock conversion/% | Glycol selectivity/% |
??A | ??160 | ??2 | ??100 | ??0.3 | ??99 | ??95 |
??B | ??193 | ??3 | ??80 | ??0.8 | ??99 | ??95 |
??C | ??180 | ??5 | ??50 | ??0.4 | ??99 | ??97 |
??D | ??250 | ??3 | ??100 | ??3.0 | ??99 | ??96 |
??E | ??215 | ??8 | ??100 | ??0.9 | ??99 | ??95 |
Conclusion: above-mentioned catalyst is applied to the reaction that oxalate or ethyl glycolate gas phase hydrogenation prepare ethylene glycol, reaction-ure conversion-age, selectivity of product and yield all calculate by carbon number, feed stock conversion is more than 99%, glycol selectivity reaches more than 95%, and described catalyst is activity stabilized through experiment in 3500 hours.
Claims (13)
1. catalyst for hydrogenation is characterized in that, chemical formula is:
CuOx-ROy/SiO
2
Wherein: SiO
2Be carrier;
R is selected from one or more in alkali earth metal, transition metal or the thulium:
X is 1/2 of a Cu valence mumber;
Y is 1/2 of a R valence mumber.
2. catalyst for hydrogenation according to claim 1 is characterized in that, is 100 parts in total catalyst weight, and the content of R element is 0~15 part, and the content of Cu element is 10~70 parts.
3. catalyst for hydrogenation according to claim 1 is characterized in that, is 100 parts in described total catalyst weight, and the content of R element is 0.01~10 part, and the content of Cu element is 15~60 parts;
4. according to claim 1,2 or 3 described catalyst for hydrogenation, it is characterized in that R is selected from one or more among Ca, Ba, Mn, Mo, Co, Zr, Zn, Pd, Ru, Pt, La, Eu or the Ce.
5. catalyst for hydrogenation according to claim 1 is characterized in that, described SiO
2For specific surface at 5m
2/ g~1000m
2In/g the scope is the setting or the amorphous materials of agent structure with Si-O.
6. catalyst for hydrogenation according to claim 1 is characterized in that, described SiO
2Derive from silica gel, diatomite, white carbon, estersil or the Ludox one or more.
7. the preparation method of each described catalyst for hydrogenation of claim 1~6 is characterized in that, in turn includes the following steps:
(1) with silicon source, water and Cu salting liquid or silicon source, Cu salting liquid and R salt solution mix, add acidity or alkaline matter, regulating the pH value is 1~6, add precipitant solution then, reaction under proper condition, control reaction solution endpoint pH is 7~14, the solid matter in the collecting reaction product;
The solid matter washing of (2) step (1) being collected, drying;
(3) product with step (2) more than 0.5 hour, obtains described catalyst 300~600 ℃ of following roastings.
8. method according to claim 7 is characterized in that, in the step (1), the reaction time is 0.5~48 hour.
9. method according to claim 7 is characterized in that, described Cu salt or R salt are selected from one or more in the water-soluble salt of nitrate, acetate or halide;
Described precipitating reagent is alkaline precipitating agent or the preformed precipitate agent that can generate alkaline matter under certain condition, includes but not limited to carbonate, ammoniacal liquor or urea;
Described acidity or alkaline matter are selected from but are not limited to inorganic acid alkali, organic acids and base or some salt;
Described felicity condition includes but not limited to stir, aging, condensing reflux.
10. method according to claim 7 is characterized in that, the weight portion consumption of each component is: SiO
2Weight portion be 1~85, the weight portion of water is 200 parts, the weight portion of precipitating reagent is 1~100, the weight portion of Cu element is 10~70, the weight portion of R element is 0~15.
11. method according to claim 7 is characterized in that, SiO
2Be 20~60 weight portions, precipitating reagent is 40~80 weight portions.
12. the application of each described catalyst for hydrogenation of claim 1~6 is characterized in that, is used for oxalate or the ethyl glycolate hydrogenation reaction prepares ethylene glycol.
13. application according to claim 11 is characterized in that application process comprises the steps:
(1) described catalyst was reduced 4~20 hours under 200~500 ℃, hydrogen atmosphere, hydrogen volume concentration is 0.5%~100%;
(2) be dissolved in the solvent with oxalate or ethyl glycolate heat fused or with it, contact with hydrogen in the presence of described catalyst then, the liquid hourly space velocity (LHSV) of oxalate or ethyl glycolate is 0.01~5.4g/g cat.h, and the hydrogen ester ratio is 20~500; Reaction temperature is 160~260 ℃, and reaction pressure is 1~10MPa.
Described solvent is including, but not limited to alcohols or ester class, and the weight content of oxalate or ethyl glycolate is 1~60%.
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102649746A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
CN102649747A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction |
WO2013020399A1 (en) * | 2011-08-10 | 2013-02-14 | 天津大学 | Catalyst for ethanol production via hydrogenation of oxalate and preparation method and use thereof |
CN103100394A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
JP2013103192A (en) * | 2011-11-15 | 2013-05-30 | Tosoh Corp | Method of manufacturing hydrogenation catalyst |
CN103721734A (en) * | 2013-12-04 | 2014-04-16 | 上海焦化有限公司 | Catalytic agent for preparing 1,3-PDO by performing hydrogenization on 3-hydracrylic acid methyl ester, and preparation and application of catalytic agent |
CN104525219A (en) * | 2015-01-04 | 2015-04-22 | 北京旭阳化工技术研究院有限公司 | Method for preparing catalyst for preparing methyl glycolate by adding hydrogen into dimethyl oxalate |
CN108126752A (en) * | 2017-11-16 | 2018-06-08 | 福州大学 | A kind of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst and its preparation method and application |
CN109833884A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of methyl glycollate hydrogenolysis prepares catalyst of ethyl alcohol and its preparation method and application |
CN111686742A (en) * | 2019-03-14 | 2020-09-22 | 上海诺哈尔化工技术有限公司 | Copper-based catalyst and preparation method thereof |
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CN102649747A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction |
CN102649747B (en) * | 2011-02-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction |
CN102649746A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
WO2013020399A1 (en) * | 2011-08-10 | 2013-02-14 | 天津大学 | Catalyst for ethanol production via hydrogenation of oxalate and preparation method and use thereof |
CN103100394B (en) * | 2011-11-09 | 2014-07-23 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
CN103100394A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
JP2013103192A (en) * | 2011-11-15 | 2013-05-30 | Tosoh Corp | Method of manufacturing hydrogenation catalyst |
CN103721734A (en) * | 2013-12-04 | 2014-04-16 | 上海焦化有限公司 | Catalytic agent for preparing 1,3-PDO by performing hydrogenization on 3-hydracrylic acid methyl ester, and preparation and application of catalytic agent |
CN103721734B (en) * | 2013-12-04 | 2016-03-23 | 上海华谊能源化工有限公司 | One is used for 3-hydroxy methyl propionate Hydrogenation for 1, the catalyst of 3 propane diols and preparation and application thereof |
CN104525219A (en) * | 2015-01-04 | 2015-04-22 | 北京旭阳化工技术研究院有限公司 | Method for preparing catalyst for preparing methyl glycolate by adding hydrogen into dimethyl oxalate |
CN108126752A (en) * | 2017-11-16 | 2018-06-08 | 福州大学 | A kind of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst and its preparation method and application |
CN109833884A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of methyl glycollate hydrogenolysis prepares catalyst of ethyl alcohol and its preparation method and application |
CN111686742A (en) * | 2019-03-14 | 2020-09-22 | 上海诺哈尔化工技术有限公司 | Copper-based catalyst and preparation method thereof |
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Application publication date: 20100616 |