CN101624330A - Method for preparing 1,4-butanediol through hydrogenation of cis-butenedioic acid dimethyl ester - Google Patents
Method for preparing 1,4-butanediol through hydrogenation of cis-butenedioic acid dimethyl ester Download PDFInfo
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- CN101624330A CN101624330A CN200810040390A CN200810040390A CN101624330A CN 101624330 A CN101624330 A CN 101624330A CN 200810040390 A CN200810040390 A CN 200810040390A CN 200810040390 A CN200810040390 A CN 200810040390A CN 101624330 A CN101624330 A CN 101624330A
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Abstract
The invention relates to a method for preparing 1,4-butanediol with co-production of tetrahydrofuran and gamma-butyrolactone through gas-phase hydrogenation of cis-butenedioic acid dimethyl ester, which comprises the following steps: gasifying the cis-butenedioic acid dimethyl ester and then contacting the gasified cis-butenedioic acid dimethyl ester with a pre-reduced catalyst comprising a component of a general formula of CuCraAlbOx, and performing hydrogenation reaction at a temperature of between 170 and 190 DEG C and at a pressure of between 4.0 and 6.0 MPa to obtain the 1,4-butanediol, the tetrahydrofuran and the gamma-butyrolactone, wherein a is equal to between 0.5 and 0.65, b is equal to between 0.01 and 0.05, and x satisfies the number of oxygen atoms of each metallic element chemical valence. The method can completely convert the raw material of the cis-butenedioic acid dimethyl ester at a high liquid hourly space velocity, and make the mol selectivities of the 1,4-butanediol, the tetrahydrofuran and the gamma-butyrolactone reach between 70 and 85 percent, between 5 to 10 percent and between 10 and 15 percent respectively.
Description
Technical field
The invention belongs to chemical technology field, particularly relate to a kind of 1, the preparation method of 4-butyleneglycol.
Background technology
1, the 4-butyleneglycol is a kind of important Organic Chemicals, is mainly used in production polybutyl terapthalate (PBT), urethane, gamma-butyrolactone and tetrahydrofuran (THF).Usually, 1, the 4-butyleneglycol is to be raw material with acetylene and formaldehyde, and is under high pressure synthetic, also can be made by gamma-butyrolactone or tetrahydrofuran (THF) hydrolysis.The development for preparing the MALEIC ANHYDRIDE technology along with butane oxidation, since the sixties, MALEIC ANHYDRIDE and ester shortening system 1 thereof, the technology of 4-butyleneglycol is few with its reactions steps, investment is low, can regulate the characteristics of products therefrom and enjoy and gaze at.Early stage MALEIC ANHYDRIDE gas phase hydrogenation method adopts Zn-Cu-Cr catalyzer (special public clear 44-32567) and CuO-BeO-ZnO catalyzer (special public clear 44-23294), but can only obtain gamma-butyrolactone and can not directly obtain 1, the 4-butyleneglycol, and to obtain 1, the 4-butyleneglycol can only by with the catalyzer that contains the VII subgroup element, liquid-phase hydrogenatin by MALEIC ANHYDRIDE realizes (spy opens clear 51-133212), but the required reaction pressure height of liquid-phase hydrogenatin technology (for example reaches 200Kg/cm
2), cause facility investment and process cost height.
Since the eighties, adopting the base metal mixed oxide is catalyzer, makes 1 from the maleate vapour phase hydrogenation, and the method development of 4-butyleneglycol is very fast, as EP0143634 disclose a kind of with the Cu-Cr-Mn mixed oxide be catalyzer at 150～240 ℃, 25～75 the crust, H
2/ ester mol ratio is 150～800: 1, and raw material liq volume charging air speed (LHSV) is 0.1～0.6 hour
-1, adopt two sections vapour phase hydrogenation methods by diethyl maleate and/diethyl succinate makes 1, the method for 4-butyleneglycol, this method result preferably is: at 170～190 ℃, 4MPa, LHSV0.34 hour
-1, H
2/ ester mol ratio is under 300: 1 conditions, and ester conversion rate is greater than 90 moles of %, 1, and the selectivity of 4-butyleneglycol just can reach 70 moles more than the %.
Japanese patent laid-open 2-25434 has proposed to use MALEIC ANHYDRIDE and/or Succinic anhydried through gas phase hydrogenation system 1, the method for 4-butyleneglycol, and reaction is a catalyzer with the ZnO-CuO after reducing, 180～280 ℃, 20～70 kg/cm
2Following enforcement, product is 1,4-butyleneglycol and tetrahydrofuran (THF) etc.When being reaction raw materials with the MALEIC ANHYDRIDE, gamma-butyrolactone is the solvent of reaction raw materials acid anhydride, is 1: 4 acid anhydride and ester charging with mol ratio, and the mol ratio of hydrogen and acid anhydride, ester is 1: 200 o'clock, 230 ℃, 40 kg/cm
2Under the condition, it is 9000 o'clock as the gaseous phase volume air speed
-1(value under the normal temperature and pressure, down together; The gaseous phase volume air speed that this value is converted into acid anhydride is 9 o'clock
-1), then the transformation efficiency of acid anhydride and ester is respectively 100% and 25.2%, for the charging total mole number, and 1,4-butyleneglycol productive rate is 31.9% (1, the selectivity of 4-butyleneglycol is 93.5%).
WO9101961 discloses the gas phase catalytic reaction device of two parallel connections of a kind of employing, makes 1 by maleate, and the method for 4-butyleneglycol, this method are compared the resistance that has reduced reactor with tandem reactor, simplified technology, but not mentioned air speed problem.
U.S. Pat 4584419 discloses a kind of Cu-Cr catalyzer and this catalyzer and has been used for vapour phase hydrogenation MALEIC ANHYDRIDE/or the technology of its ester.But because catalyst activity is low, need to adopt the multistage hydrogenation just can obtain target product 1,4-butyleneglycol, and the content height of by product propyl carbinol cause product yield low.It is many that the polymeric by product takes place, have can also with product 1, the 4-butyleneglycol forms azeotrope, has increased the separation difficulty of postorder.
In a word, existing be used for MALEIC ANHYDRIDE and/or its ester gas phase hydrogenation system 1, there is following shortcoming in the catalyzer of 4-butyleneglycol:
1, in certain raw material air speed scope, can both make almost 100 moles of % of transformation efficiency, but 1, the selectivity of 4-butyleneglycol but raises with the raw material air speed and descends rapidly, when the gaseous phase volume air speed of raw material acid anhydride is increased to 20
-1When above, 1 of existing catalyzer, 4-butyleneglycol selectivity can only reach 50～60 moles of %.
2, unreacted raw material or by product need carry out circulating reaction after separating, purifying, and the ester interchange polymerization reaction easily takes place in the circulation of this High Temperature High Pressure these materials, causes product yield to reduce.
3, starting ester generally is to get through the cis-butenedioic anhydride esterification, have certain acidity, must select a kind of not only antiacid but also can be, but it be higher to have the catalyst activity of this performance usually the catalyzer of sour hydrogenation, the processing condition temperature height, the pressure height that use make ester cross hydrogenation and generate propyl carbinol, tetrahydrofuran (THF).
4, how many dimethyl succinate amounts of dimethyl maleate reaction generation directly determines selectivity of catalyst and work-ing life.Because ester interchange polymerization easily takes place and covers catalyst surface in its ester, cause catalyst deactivation, and add component aluminium, can improve the dimethyl succinate transformation efficiency, reduce the particularly generation of dimethyl succinate of by product, improved catalyst selectivity and life-span.
Summary of the invention
Technical problem to be solved
It is raw material with the dimethyl maleate that technical problem to be solved by this invention provides a kind of, the use non-precious metal catalyst, carry out one section gas phase catalytic hydrogenation prepared in reaction 1, the method of 4-butyleneglycol, to overcome prior art to the dimethyl maleate reaction not exclusively, particularly the dimethyl succinate generation is many for by product, need carry out circulating reaction, raw material liq volume charging air speed is lower, and the defective of tool reaction stability difference.
Technical scheme
The invention provides a kind of dimethyl maleate gas phase hydrogenation preparation 1, the method for 4-butanediol-coproduced tetrahydro furan and gamma-butyrolactone, step comprises: after the dimethyl maleate gasification, with the CuCr that has of pre-reduction
aAl
bO
xThe catalyzer contact that general formula is formed is carried out hydrogenation reaction and is obtained 1,4-butyleneglycol, tetrahydrofuran (THF) and gamma-butyrolactone under 170～190 ℃, 4.0～6.0MPa pressure condition; Wherein, a=0.5～0.65, b=0.01～0.05, x is for satisfying the valent oxygen atomicity of each metallic element.
One of preferred version of above-mentioned method is, the mol ratio of hydrogen and dimethyl maleate is 150～400: 1 during described hydrogenation reaction, is preferably 150～250: 1.
Two of the preferred version of above-mentioned method is that the liquid hourly space velocity of the dimethyl maleate of described hydrogenation reaction is 0.18～0.42 hour
-1
Three of the preferred version of above-mentioned method is, described catalyzer is that the precursor with Cu, Cr makes through co-precipitation in the presence of alkali, and perhaps Cu, Cr are after co-precipitation, and the aluminium source adds with solid form.Preferably, the precursor of described Cu, Cr is a nitrate separately, or Cr is dichromate, or Al is an oxyhydroxide; Preferably, described alkali is selected from ammoniacal liquor, urea or yellow soda ash, more preferably ammoniacal liquor; Preferably, the pH value of described co-precipitation is 5.0～7.0.
Four of the preferred version of above-mentioned method is that described step also comprises: before reaction with described catalyzer as antiacid catalyzer, share with the ester through hydrogenation catalyzer, the acidic substance hydrogenation that exists in the described dimethyl maleate.
Five of the preferred version of above-mentioned method is, the pre-reduction method of described catalyzer is to adopt reducing gas as reductive agent, under 0.1～3.0MPa pressure, to the flow velocity feeding reducing gas of every milliliter of catalyzer, reduced 6～16 hours down at 150～250 ℃ with 50～100 ml/min.
The used dimethyl maleate of the present invention need gasify before reaction, the mode of the available routine that gasifies is carried out, as in packing tower, the liquid dimethyl maleate gasifies in reverse the contact with the hydrogen stream of heat, reaches to enter reactor and catalyzer contact reacts after meeting temperature of reaction.
Carry out for making to be reflected under the gas phase, temperature of reaction must be higher than the dew point of reactant under this reaction conditions, reaction temperature is spent low, even be higher than the dew point of reactant, transformation efficiency is descended, and too high temperature of reaction can produce by products such as tetrahydrofuran (THF), butanols, so the suitable temperature of reaction that the present invention selects is 170～190 ℃.
For hydrogenation reaction, pressure boost helps improving the transformation efficiency of dimethyl maleate, but too high pressure will make energy consumption increase, and increases facility investment and process cost, and for ease of suitability for industrialized production, the suitable pressure of selection is 4.0～6.0MPa.
Excessive hydrogen helps the conversion of dimethyl maleate in the reaction system, and raw material is gasified under lower temperature, but hydrogen is excessive too many, will reduce the duration of contact of ester and catalyzer, cause 1,4-butyleneglycol selectivity descends, and increase system energy consumption, so selecting the hydrogen ester mol ratio among the present invention is 150～400: 1, is preferably 150～250: 1, reaction back the exess of H2 gas can recycle.
In one embodiment of the invention, described catalyzer adopts conventional coprecipitation method preparation: after soon the soluble salt of Cu, Cr, Al will be made mixed solution, adding alkali to pH value is 5.0～6.0, collecting precipitation (the soluble salt that also can not add Al earlier, press above-mentioned steps after the mixed solution of Cu, Cr is transferred pH to 5.0～6.0, in solution, add solid aluminium source, thorough mixing after scouring, filtration).At last, 100～200 ℃ of dryings 8～12 hours, 350～600 ℃ of roastings promptly got catalyzer in 3～10 hours.
Catalyzer of the present invention needs to reduce in advance before use, and reductive agent can adopt H
2, reducing gas such as carbon monoxide, also can be with inert gas dilution reducing gas.Reduction can be undertaken by following method, for example, under 0.1～3.0MPa pressure, to the flow velocity feeding reducing gas of every milliliter of catalyzer with 50～100 ml/min, reduces 6～16 hours down at 150～250 ℃.
Beneficial effect
In the inventive method owing to used Cu, Cr, the Al catalyzer of specific composition, make up with specific reaction conditions, make dimethyl maleate under higher raw material air speed, to transform fully, and obtain higher 1,4-butanediol-coproduced tetrahydro furan, gamma-butyrolactone selectivity, by product is few, and is easily separated.With another kind of CuCr
aO
xThe catalyzer of two components is compared, and the mass content of by product dimethyl succinate is reduced to 0.2% from 0.5%, thereby has improved the work-ing life and the stability of catalyzer.As the raw material volume space velocity is 0.42 hour
-1Transformation efficiency reaches 100 moles of %, 1,4-butyleneglycol selectivity is not less than 70 moles of %, in addition, Cu-Cr-Mn-Ba four component catalysts that disclose in three component catalysts that adopt in the inventive method and the prior art compare 1, the selectivity of 4-butyleneglycol has raising by a relatively large margin, illustrates that the catalyzer that uses in the reaction method of the present invention has good catalytic performance.
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 catalyzer or chemical industry operation handbook, or the condition of advising according to manufacturer.Cu (NO
3)
23H
2O is from prosperous fine chemicals company of section, analytical pure; Cr (NO
3)
39H
2O is from Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure; Al (NO
3)
39H
2O is from the Shanghai glad chemical reagent work of shaking, analytical pure; Ammoniacal liquor is from Shanghai chemical reagent work; Na
2CO
3From last marine rainbow photoinitiator chemical factory, analytical pure; Urea is from Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure.
Embodiment 1
With 40 gram Cu (NO
3)
23H
2O (prosperous fine chemicals company of section, analytical pure), 43.0 gram Cr (NO
3)
39H
2O (Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure), 1.24 gram Al (NO
3)
39H
2O (the Shanghai glad chemical reagent work of shaking, analytical pure) is dissolved in 600 ml deionized water, after stirring, ammoniacal liquor (Shanghai chemical reagent work produces, concentration 23～25 heavy %) is splashed in the mixing salt solution with peristaltic pump, until pH is 5.5 ± 0.2, filtration washing, collecting precipitation, 100 ℃ of dried overnight, 500 ℃ of roastings 10 hours, moulding makes catalyst Precursors then.Promptly get catalyst A: CuCr
0.65Al
0.02O
2.02
Embodiment 2
By the Cu/Cr mol ratio is 0.65 metering, earlier the 1M copper nitrate aqueous solution is mixed with strong aqua, makes pH and be 11 cupric ammine complex solution.Under agitation ammonium dichromate (Ling Feng chemical reagent factory, the analytical pure) aqueous solution (pH=4) of 1M is splashed in the cupric ammine complex then.Treat that ammonium dichromate aqueous solution splashes into a half, the pH to 6 with concentrated nitric acid accent reaction solution continues to splash into second half ammonium dichromate aqueous solution again.The entire reaction temperature is 50 ℃.After dropwising, stirred down aging 3 hours, filter then, with distilled water wash gained precipitation, until no NO at 50 ℃
3 -Till, in solution, add 0.52 gram Al (OH)
3Fully stir after-filtration, 100 ℃ of dried overnight of filter cake, 500 ℃ of roastings 10 hours, moulding makes catalyst Precursors then.Promptly get catalyst B: CuCr
0.65Al
0.04O
2.08
Embodiment 3
With 40 gram Cu (NO
3)
23H
2O (Shanghai chemical reagent work produces, analytical pure), 33.1 gram Cr (NO
3)
39H
2O (Shanghai chemical reagent work produces, analytical pure), 51.96 gram urea are dissolved in 500 ml deionized water, after stirring, stir down at 90 ℃, and ageing 24 hours is 6.5 ± 0.2 until pH, adds 0.26 gram Al (OH) in solution
3Fully stir after scouring, filtration, 100 ℃ of dried overnight of filter cake, 500 ℃ of roastings 10 hours, moulding makes catalyst Precursors then.Promptly get catalyzer C:CuCr
0.5Al
0.02O
1.78
Following comparative example 4～6 is not within the scope of the invention.
Embodiment 4
With 40 gram Cu (NO
3)
23H
2O, 43.0 gram Cr (NO
3)
39H
2O is dissolved in 600 ml deionized water, and after stirring, (concentration 23～25wt%) splashes in the mixing salt solution with ammoniacal liquor with peristaltic pump, until pH is 5.5 ± 0.2, filtration washing, collecting precipitation, 100 ℃ of dried overnight, 500 ℃ of roastings 10 hours, moulding makes catalyst Precursors then.Promptly get catalyzer D:CuCr
0.65O
2
Embodiment 5
By the Cu/Cr mol ratio is 0.65 metering, earlier the 1M copper nitrate aqueous solution is mixed with strong aqua, makes pH and be 11 cupric ammine complex solution.Under agitation ammonium dichromate (Ling Feng chemical reagent factory, the analytical pure) aqueous solution (pH=4) of 1M is splashed in the cupric ammine complex then.Treat that ammonium dichromate aqueous solution splashes into a half, the pH to 6 with concentrated nitric acid accent reaction solution continues to splash into second half ammonium dichromate aqueous solution again.The entire reaction temperature is 50 ℃.After dropwising, stirred down aging 3 hours, filter then, with distilled water wash gained precipitation, until no NO at 50 ℃
3 -Till, filter, 100 ℃ of dried overnight of filter cake, 500 ℃ of roastings 10 hours, moulding makes catalyst Precursors then.Promptly get catalyzer E:CuCr
0.65O
2
Embodiment 6
With 20 gram Cu (NO
3)
23H
2O, 16.55 gram Cr (NO
3)
39H
2O, 25.98 gram urea are dissolved in 500 ml deionized water, after stirring, stir down at 90 ℃, ageing 24 hours is 6.5 ± 0.2 until pH, filtration washing, collecting precipitation, 100 ℃ of dried overnight, 500 ℃ of roastings 10 hours, moulding makes catalyst Precursors then.Promptly get catalyzer F:CuCr
0.5O
1.75
Embodiment 7
Before the dimethyl maleate hydrogenation reaction, catalyst A or B or C are layered on above the ester through hydrogenation catalyzer, as antiacid catalyzer in advance a small amount of acidic substance hydrogenation that exists in the dimethyl maleate, to improve ester through hydrogenation selectivity of catalyst and work-ing life.
Embodiment 8
Getting granularity is 2 milliliters of 40～60 purpose A catalyzer, the internal diameter of packing into is 10 millimeters, length is in 100 millimeters the stainless steel tubular type reactor, use the nitrogen purging reactive system, and with the reactive system pressurising to 0.1MPa, feed hydrogen with 300 milliliters/hour flow to reactive system then, with 10 ℃/hour average temperature rise rate reactor is risen to 180 ℃ by room temperature simultaneously, and kept 12 hours at 180 ℃.Bed temperature is transferred to 185 ℃, pressure transfer to 5.0MPa, the stable back charging of system, charging is 1: 4 dimethyl maleate of mol ratio (note is made DMM) and solvent methanol, and the hydrogen ester mol ratio is 185: 1, and the liquid hourly space velocity of DMM is 0.18 hour
-1, the product gas chromatographic analysis, the transformation efficiency that records DMM is 100%, 1, and the mole selectivity of 4-butyleneglycol is 75.3%, and the mole selectivity of tetrahydrofuran (THF) is 10.9%, and the mole selectivity of gamma-butyrolactone is 13.2%.Compare with using the Cu-Cr catalyzer D do not add aluminium under the same reaction conditions, the content of by product dimethyl succinate reduces to 0.2% by original 0.5%.
Embodiment 9
Get catalyst B, operate according to the mode of embodiment 4, different is is adjusted into 175 ℃, pressure with temperature of reaction and transfers to 6.0MPa.Use gas chromatographic analysis, the transformation efficiency that records DMM is 100%, 1, and the mole selectivity of 4-butyleneglycol is 74.3%, and the mole selectivity of tetrahydrofuran (THF) is 10.5%, and the mole selectivity of gamma-butyrolactone is 14.5%.Compare with using the Cu-Cr catalyzer E do not add aluminium under the same reaction conditions, the content of by product dimethyl succinate reduces to 0.1% by original 0.45%.
Embodiment 10
Get catalyzer C, operate according to the mode of embodiment 4, the volume space velocity of different is ester is 0.24 hour
-1, the hydrogen ester mol ratio is 250: 1, gas chromatographic analysis, and the transformation efficiency that records DMM is 100%, 1, and the mole selectivity of 4-butyleneglycol is 76.2%, and the mole selectivity of tetrahydrofuran (THF) is 8.9%, and the mole selectivity of gamma-butyrolactone is 13.9%.Compare with using the Cu-Cr catalyzer F do not add aluminium under the same reaction conditions, the content of by product dimethyl succinate reduces to 0.15% by original 0.51%.
Claims (10)
1. dimethyl maleate gas phase hydrogenation preparation 1, the method for 4-butanediol-coproduced tetrahydro furan and gamma-butyrolactone, step comprises: after the dimethyl maleate gasification, with the CuCr that has of pre-reduction
aAl
bO
xThe catalyzer contact that general formula is formed is carried out hydrogenation reaction and is obtained 1,4-butyleneglycol, tetrahydrofuran (THF) and gamma-butyrolactone under 170～190 ℃, 4.0～6.0MPa pressure condition; Wherein, a=0.5～0.65, b=0.01～0.05, x is for satisfying the valent oxygen atomicity of each metallic element.
2. method according to claim 1 is characterized in that, the mol ratio of hydrogen and dimethyl maleate is 150～400: 1 during described hydrogenation reaction.
3. method according to claim 1 is characterized in that, the mol ratio of hydrogen and dimethyl maleate is 150～250: 1 during described hydrogenation reaction.
4. method according to claim 1 is characterized in that, the liquid hourly space velocity of the dimethyl maleate of described hydrogenation reaction is 0.18～0.42 hour
-1
5. method according to claim 1 is characterized in that, described catalyzer is respectively the precursor of Cu, Cr, Al to be made through co-precipitation in the presence of alkali, and perhaps Cu, Cr are after co-precipitation, and the aluminium source adds with solid form.
6. method according to claim 5 is characterized in that, the precursor of described Cu, Cr, Al is a nitrate separately, or Cr is dichromate, or Al is an oxyhydroxide.
7. method according to claim 5 is characterized in that described alkali is selected from ammoniacal liquor, urea or yellow soda ash.
8. method according to claim 5 is characterized in that, the pH value of described co-precipitation is 5.0～7.0.
9. method according to claim 1 is characterized in that, described step also comprises: before reaction with described catalyzer as antiacid catalyzer, share with the ester through hydrogenation catalyzer, the acidic substance hydrogenation that exists in the described dimethyl maleate.
10. method according to claim 1, it is characterized in that, the pre-reduction method of described catalyzer is, adopt reducing gas as reductive agent, under 0.1～3.0MPa pressure, to the flow velocity feeding reducing gas of every milliliter of catalyzer, reduced 6～16 hours down at 150～250 ℃ with 50～100 ml/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671671A (en) * | 2012-06-04 | 2012-09-19 | 盐城工学院 | Catalyst and application thereof to synthesis of o-hydroxyphenyl ether |
| CN103769157A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN108114727A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
-
2008
- 2008-07-09 CN CN200810040390A patent/CN101624330A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671671A (en) * | 2012-06-04 | 2012-09-19 | 盐城工学院 | Catalyst and application thereof to synthesis of o-hydroxyphenyl ether |
| CN103769157A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103769157B (en) * | 2012-10-24 | 2015-07-22 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN108114727A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
| CN108114727B (en) * | 2016-11-28 | 2020-08-11 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
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Application publication date: 20100113 |