CN104307557A - Preparation method of catalyst for methyl difluoroacetate hydrogenation to produce difluoroethanol - Google Patents
Preparation method of catalyst for methyl difluoroacetate hydrogenation to produce difluoroethanol Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst for methyl difluoroacetate hydrogenation to produce difluoroethanol. The method comprises the following specific steps: first adding vanadic anhydride and NbCl3 by weight into an alkali solution, adding with heating and stirring polypropylene glycol and tetraethoxysilane, continuing stirring for 20-30 min, filtering the precipitate, rinsing with deionized water, drying, adding the dried solid with potassium oxide, calcium tungstate, zinc oxide and zeolite powder together into a saturated solution of calcium chloride, stirring to mix well, heating up to 50-60 DEG C, adding a potassium permanganate solution, stirring for 1-2 h, cooling to room temperature, filtering out the precipitate, cleaning with deionized water, and then sintering at 600-700 DEG C, cleaning the cured substances after sintering with deionized water, and drying to constant weight. The catalyst prepared by the invention has high efficiency catalysis capability and catalysis stability under normal pressure.
Description
Technical field
The invention belongs to chemical catalyst preparing technical field, be specifically related to the preparation method of a kind of methyl difluoroacetate Hydrogenation for the catalyst of difluoroethanol.
Background technology
Difluoroethanol is due to containing difluoromethyl, therefore there is the performance different from other fluorine-containing alcohols, be mainly used in the intermediate of medicine, agricultural chemicals, and for killing rodent, its derivative can kill some plants or plant insect as herbicide and pesticide.
It is very important synthesis link in Chemical Manufacture that ester through hydrogenation produces corresponding alcohol, normal employing Cu catalyst and VIII B metallic catalyst.Christiansen is after Material synthesis alcohol first with methyl formate on copper-based catalysts, and researcher just starts to have done large quantity research to such catalyst.Although Cu catalyst also has good ester through hydrogenation performance, catalysqt deactivation limits his scope.Numerous research shows, Cu-Cr catalyst is produced alcohol to ester through hydrogenation and had well active and very high selective.There is the loss of Cr6+ during Cu-Cr catalyst not enough in preparation process, cause environmental pollution.For this reason, increasing researcher is more prone to the ester class hydrogenation reaction research of noble metal catalyst.Shin-ichi Taniguchi etc. adds Pt to Ru-Sn catalyst and is successfully acted on the reaction of Hydrogenation fatty alcohol, and reaction temperature obviously reduces.In the technical process of synthesis fluorine alcohol, fluorine-containing carboxylic acid ester hydrogenation is an important synthetic route, and Willenberg is with CuO, ZnO, Al
2o
3, Cr
2o
3deng hopcalite catalyst the most, under pressure 2bar, reaction temperature 115-200 DEG C condition, achieve the liquid-phase hydrogenatin to trifluoro-acetate.In addition, E.I.Du Pont Company with copper chromate 10-80bar, 30-300 DEG C and palladium under 20-60bar, 70-175 DEG C of condition for trifluoro-acetate and trifluoroacetic acid hydrogenation synthesis trifluoroethanol; Buyle Olivier etc. are that raw material carries out liquid-phase hydrogenatin by Rh/C catalyst and synthesizes difluoroethanol under 40bar, 90 DEG C of conditions with methyl difluoroacetate.
Although the catalyst of existing a lot of synthesis difluoroethanol at present, but mostly exist under needing high temperature, high pressure and carry out liquid phase reactor, simultaneously the lower and catalyst of catalytic reaction conversion ratio requires higher to reaction condition, the shortcoming such as catalyst poor stability under differential responses condition, make continuous seepage control not easily to carry out, be therefore necessary to carry out further research and development.
Summary of the invention
The object of the invention is to provide a kind of methyl difluoroacetate Hydrogenation for the preparation method of the catalyst of difluoroethanol to overcome above the deficiencies in the prior art, realize catalyzing and synthesizing difluoroethanol under low-temperature atmosphere-pressure condition, improve catalyst stability and conversion ratio simultaneously.
The present invention is realized by following technological means:
Methyl difluoroacetate Hydrogenation, for a preparation method for the catalyst of difluoroethanol, comprises the following steps:
Step one, in components by weight percent, by 2-5 part vanadic anhydride and 2-5 part NbCl
3joining mass percent is in the aqueous slkali of 6-10%, is heated to 30-40 DEG C, under stirring, then add 0.8-2 part polypropylene glycol and 1-5 part tetraethyl orthosilicate, continue after adding to stir 20-30 minute, then by sedimentation and filtration, clean with deionized water rinsing, dry;
Step 2, in components by weight percent, solids after step one being dried and 2-6 part potassium oxide, 0.5-1 part artificial schellite, 1-5 part zinc oxide join in 10-20 part calcium chloride saturated solution together with 6-15 part zeolite powder, be uniformly mixed, be warming up to 50-60 DEG C, add 1-2 part liquor potassic permanganate, stirring reaction 1-2 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, be then sinter under the condition of 600-700 DEG C in temperature, solidfied material after sintering is clean by washed with de-ionized water, dry to constant weight.
Described methyl difluoroacetate Hydrogenation is for the preparation method of the catalyst of difluoroethanol, and in step one, aqueous slkali can be NaOH or potassium hydroxide solution.
Described methyl difluoroacetate Hydrogenation is for the preparation method of the catalyst of difluoroethanol, and step 2 mesolite Powder Particle Size can be 500-800 μm.
Described methyl difluoroacetate Hydrogenation is for the preparation method of the catalyst of difluoroethanol, and in step one, the granularity of vanadic anhydride can be 100-300 μm.
Described methyl difluoroacetate Hydrogenation is for the preparation method of the catalyst of difluoroethanol, and in step 2, the granularity of artificial schellite can be 100-300 μm.
Described methyl difluoroacetate Hydrogenation is for the preparation method of the catalyst of difluoroethanol, and in step 2, liquor potassic permanganate concentration can be 5-10%.
Described methyl difluoroacetate Hydrogenation is for the preparation method of the catalyst of difluoroethanol, and in step 2, sintering time can be 3-5 hour.
The catalyst that methyl difluoroacetate Hydrogenation provided by the invention prepares for the preparation method of the catalyst of difluoroethanol reaches more than 98.6% for the conversion ratio of methyl difluoroacetate, difluoroethanol yield reaches more than 55.6%, selectively reach more than 99.1%, show that methyl difluoroacetate Hydrogenation provided by the invention has efficient catalytic capability for the catalyst of difluoroethanol.
Detailed description of the invention
Embodiment 1
Methyl difluoroacetate Hydrogenation, for a preparation method for the catalyst of difluoroethanol, comprises the following steps:
Step one, in components by weight percent, by 2 parts of vanadic anhydrides (granularity 100 μm) and 2 parts of NbCl
3joining mass percent is in the sodium hydroxide solution of 6%, is heated to 30 DEG C, under stirring, then add 0.8 part of polypropylene glycol and 1 part of tetraethyl orthosilicate, stirring is continued 20 minutes after adding, then by sedimentation and filtration, clean with deionized water rinsing, dry;
Step 2, in components by weight percent, solids after step one is dried and 2 parts of potassium oxides, 0.5 part of artificial schellite (granularity 100 μm), 1 part of zinc oxide joins in 10 parts of calcium chloride saturated solutions together with 6 parts of zeolite powders (granularity 500 μm), be uniformly mixed, be warming up to 50 DEG C, adding 1 part of concentration is the liquor potassic permanganate of 7%, stirring reaction 1 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, then be sinter 3 hours under the condition of 600 DEG C in temperature, by clean for the solidfied material washed with de-ionized water after sintering, dry to constant weight.
Embodiment 2
Methyl difluoroacetate Hydrogenation, for a preparation method for the catalyst of difluoroethanol, comprises the following steps:
Step one, in components by weight percent, by 3 parts of vanadic anhydrides (granularity 200 μm) and 3 parts of NbCl
3joining mass percent is in the potassium hydroxide solution of 7%, is heated to 33 DEG C, under stirring, then add 1 part of polypropylene glycol and 2 parts of tetraethyl orthosilicates, stirring is continued 25 minutes after adding, then by sedimentation and filtration, clean with deionized water rinsing, dry;
Step 2, in components by weight percent, solids after step one is dried and 4 parts of potassium oxides, 0.6 part of artificial schellite (granularity 150 μm), 3 parts of zinc oxide join in 12 parts of calcium chloride saturated solutions together with 8 parts of zeolite powders (granularity 600 μm), be uniformly mixed, be warming up to 52 DEG C, adding 1 part of concentration is the liquor potassic permanganate of 5%, stirring reaction 1 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, then be sinter 3 hours under the condition of 600 DEG C in temperature, by clean for the solidfied material washed with de-ionized water after sintering, dry to constant weight.
Embodiment 3
Methyl difluoroacetate Hydrogenation, for a preparation method for the catalyst of difluoroethanol, comprises the following steps:
Step one, in components by weight percent, by 4 parts of vanadic anhydrides (granularity 100 μm) and 3 parts of NbCl
3joining mass percent is in the sodium hydroxide solution of 8%, is heated to 36 DEG C, under stirring, then add 1.5 parts of polypropylene glycols and 3 parts of tetraethyl orthosilicates, stirring is continued 30 minutes after adding, then by sedimentation and filtration, clean with deionized water rinsing, dry;
Step 2, in components by weight percent, solids after step one is dried and 5 parts of potassium oxides, 0.8 part of artificial schellite (granularity 100 μm), 5 parts of zinc oxide join in 18 parts of calcium chloride saturated solutions together with 12 parts of zeolite powders (granularity 700 μm), be uniformly mixed, be warming up to 60 DEG C, adding 2 parts of concentration is the liquor potassic permanganate of 6%, stirring reaction 1 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, then be sinter 4 hours under the condition of 650 DEG C in temperature, by clean for the solidfied material washed with de-ionized water after sintering, dry to constant weight.
Embodiment 4
Methyl difluoroacetate Hydrogenation, for a preparation method for the catalyst of difluoroethanol, comprises the following steps:
Step one, in components by weight percent, by 5 parts of vanadic anhydrides (granularity 300 μm) and 4 parts of NbCl
3joining mass percent is in the potassium hydroxide solution of 10%, is heated to 38 DEG C, under stirring, then add 1.6 parts of polypropylene glycols and 4 parts of tetraethyl orthosilicates, stirring is continued 30 minutes after adding, then by sedimentation and filtration, clean with deionized water rinsing, dry;
Step 2, in components by weight percent, solids after step one is dried and 6 parts of potassium oxides, 1 part of artificial schellite (granularity 200 μm), 4 parts of zinc oxide join in 16 parts of calcium chloride saturated solutions together with 14 parts of zeolite powders (granularity 700 μm), be uniformly mixed, be warming up to 55 DEG C, adding 2 parts of concentration is the liquor potassic permanganate of 8%, stirring reaction 1 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, then be sinter 4 hours under the condition of 700 DEG C in temperature, by clean for the solidfied material washed with de-ionized water after sintering, dry to constant weight.
Embodiment 5
Methyl difluoroacetate Hydrogenation, for a preparation method for the catalyst of difluoroethanol, comprises the following steps:
Step one, in components by weight percent, by 5 parts of vanadic anhydrides (granularity 300 μm) and 5 parts of NbCl
3joining mass percent is in the sodium hydroxide solution of 10%, is heated to 40 DEG C, under stirring, then add 2 parts of polypropylene glycols and 5 parts of tetraethyl orthosilicates, stirring is continued 30 minutes after adding, then by sedimentation and filtration, clean with deionized water rinsing, dry;
Step 2, in components by weight percent, solids after step one is dried and 6 parts of potassium oxides, 1 part of artificial schellite (granularity 300 μm), 5 parts of zinc oxide join in 20 parts of calcium chloride saturated solutions together with 15 parts of zeolite powders (granularity 800 μm), be uniformly mixed, be warming up to 60 DEG C, adding 2 parts of concentration is the liquor potassic permanganate of 10%, stirring reaction 2 hours, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, then be sinter 5 hours under the condition of 700 DEG C in temperature, by clean for the solidfied material washed with de-ionized water after sintering, dry to constant weight.
In order to further illustrate the performance characteristics of the catalyst that method provided by the invention prepares, carry out the parallel test of following reference examples:
Reference examples 1
The methyl difluoroacetate Hydrogenation provided according to embodiment 3, for the preparation method of the catalyst of difluoroethanol, does not add polypropylene glycol in step one, and other conditions are identical with embodiment 3, and detailed process is as follows:
Step one, in components by weight percent, by 4 parts of vanadic anhydrides (granularity 100 μm) and 3 parts of NbCl
3joining mass percent is in the sodium hydroxide solution of 8%, is heated to 36 DEG C, then under stirring, adds 3 parts of tetraethyl orthosilicates, continues stirring 30 minutes after adding, then by sedimentation and filtration, clean with deionized water rinsing, dries;
Step 2, in components by weight percent, solids after step one is dried and 5 parts of potassium oxides, 0.8 part of artificial schellite (granularity 100 μm), 5 parts of zinc oxide join in 18 parts of calcium chloride saturated solutions together with 12 parts of zeolite powders (granularity 700 μm), be uniformly mixed, be warming up to 60 DEG C, adding 2 parts of concentration is the liquor potassic permanganate of 6%, stirring reaction 1 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, then be sinter 4 hours under the condition of 650 DEG C in temperature, by clean for the solidfied material washed with de-ionized water after sintering, dry to constant weight.
Reference examples 2
The methyl difluoroacetate Hydrogenation provided according to embodiment 3, for the preparation method of the catalyst of difluoroethanol, does not add tetraethyl orthosilicate in step one, and other conditions are identical with embodiment 3, and detailed process is as follows:
Step one, in components by weight percent, by 4 parts of vanadic anhydrides (granularity 100 μm) and 3 parts of NbCl
3joining mass percent is in the sodium hydroxide solution of 8%, is heated to 36 DEG C, then under stirring, adds 1.5 parts of polypropylene glycols, continues stirring 30 minutes after adding, then by sedimentation and filtration, clean with deionized water rinsing, dries;
Step 2, in components by weight percent, solids after step one is dried and 5 parts of potassium oxides, 0.8 part of artificial schellite (granularity 100 μm), 5 parts of zinc oxide join in 18 parts of calcium chloride saturated solutions together with 12 parts of zeolite powders (granularity 700 μm), be uniformly mixed, be warming up to 60 DEG C, adding 2 parts of concentration is the liquor potassic permanganate of 6%, stirring reaction 1 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, then be sinter 4 hours under the condition of 650 DEG C in temperature, by clean for the solidfied material washed with de-ionized water after sintering, dry to constant weight.
Reference examples 3
The methyl difluoroacetate Hydrogenation provided according to embodiment 3, for the preparation method of the catalyst of difluoroethanol, does not add calcium chloride saturated solution in step 2, and other conditions are identical with embodiment 3, and detailed process is as follows:
Step one, in components by weight percent, by 4 parts of vanadic anhydrides (granularity 100 μm) and 3 parts of NbCl
3joining mass percent is in the sodium hydroxide solution of 8%, is heated to 36 DEG C, under stirring, then add 1.5 parts of polypropylene glycols and 3 parts of tetraethyl orthosilicates, stirring is continued 30 minutes after adding, then by sedimentation and filtration, clean with deionized water rinsing, dry;
Step 2, in components by weight percent, solids after step one being dried and 5 parts of potassium oxides, 0.8 part of artificial schellite (granularity 100 μm), 5 parts of zinc oxide and 12 parts of zeolite powders (granularity 700 μm) are uniformly mixed, be warming up to 60 DEG C, adding 2 parts of concentration is the liquor potassic permanganate of 6%, stirring reaction 1 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, then be sinter 4 hours under the condition of 650 DEG C in temperature, the solidfied material after sintering is clean by washed with de-ionized water, dry to constant weight.
Performance test:
1. catalytic performance test
The catalyst above embodiment and reference examples prepared carries out the reaction of catalysis methyl difluoroacetate Hydrogenation for difluoroethanol, reaction condition is 30 DEG C, under normal pressure, detecting catalyst, for methyl difluoroacetate conversion ratio and difluoroethanol yield and selective, the results are shown in Table 1.
The catalyst performance test that table 1 embodiment 1-5 and reference examples 1-3 prepares
| Pilot project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Reference examples 1 | Reference examples 2 | Reference examples 3 |
| Conversion ratio/% | 98.6 | 99.6 | 99.9 | 99.7 | 99.2 | 95.1 | 91.2 | 88.3 |
| Yield/% | 55.6 | 56.5 | 58.9 | 58.3 | 57.8 | 40.5 | 45.5 | 36.2 |
| Selective/% | 99.1 | 99.4 | 99.8 | 99.8 | 99.5 | 86.8 | 88.6 | 79.6 |
As can be seen from above result of the test, the catalyst that embodiment prepares reaches more than 98.6% for the conversion ratio of methyl difluoroacetate, difluoroethanol yield reaches more than 55.6%, selectively reach more than 99.1%, show that methyl difluoroacetate Hydrogenation provided by the invention has efficient catalytic capability for the catalyst of difluoroethanol, wherein in embodiment 3, catalytic performance is best, therefore can as most preferred embodiment; And owing to adding certain component in preparation process less in reference examples, final catalytic performance is caused to decline, as conversion ratio when step one in reference examples 1 does not add the catalyst reaction that polypropylene glycol causes finally obtaining, product yield and selectively have obvious decline, wherein product yield and the selective decline of reactant particularly evident, show the introducing of polypropylene glycol can significantly improve the yield of catalytic reaction and reactant selective; In step one, tetraethyl orthosilicate is not added in reference examples 2, catalyst reacting catalytic performance is caused to decline, wherein conversion ratio declines especially obvious, reason is add tetraethyl orthosilicate can to make to adulterate more equably slaine in step 2 and metal oxide with polypropylene glycol, make catalyst structure homogeneous, better can play catalytic action; In step 2, calcium chloride saturated solution is not added in reference examples 3, conversion ratio when result causes catalyst to react, product yield and to be selectively all decreased significantly, reason is in the process of Kaolinite Preparation of Catalyst, adding calcium chloride saturated solution in step 2 can make solid particle can disperse to greatest extent and be fixed in the zeolite powder as carrier by the effect of calcium ion, better plays catalytic action.
2. catalyst stability test
The catalyst above embodiment prepared carries out catalytic performance test under condition of different temperatures, and reaction pressure is normal pressure, and test event is methyl difluoroacetate conversion ratio and difluoroethanol yield, the results are shown in Table 2.
The catalyst stability test that table 2 embodiment 1-5 prepares
As can be seen from above temperature stability test result, catalyst provided by the invention can not have difference substantially at catalytic performance under condition of different temperatures, can both play highly stable catalytic performance.
The catalyst that methyl difluoroacetate Hydrogenation provided by the invention prepares for the preparation method of the catalyst of difluoroethanol has excellent catalytic performance, overcome the reaction condition that must need HTHP in prior art simultaneously, catalyst performance stabilised, can adapt to different reaction temperatures simultaneously.
Claims (7)
1. methyl difluoroacetate Hydrogenation is for a preparation method for the catalyst of difluoroethanol, it is characterized in that, comprises the following steps:
Step one, in components by weight percent, by 2-5 part vanadic anhydride and 2-5 part NbCl
3joining mass percent is in the aqueous slkali of 6-10%, is heated to 30-40 DEG C, under stirring, then add 0.8-2 part polypropylene glycol and 1-5 part tetraethyl orthosilicate, continue after adding to stir 20-30 minute, then by sedimentation and filtration, clean with deionized water rinsing, dry;
Step 2, in components by weight percent, solids after step one being dried and 2-6 part potassium oxide, 0.5-1 part artificial schellite, 1-5 part zinc oxide join in 10-20 part calcium chloride saturated solution together with 6-15 part zeolite powder, be uniformly mixed, be warming up to 50-60 DEG C, add 1-2 part liquor potassic permanganate, stirring reaction 1-2 hour, be down to room temperature, precipitation is leached, clean by washed with de-ionized water, be then sinter under the condition of 600-700 DEG C in temperature, solidfied material after sintering is clean by washed with de-ionized water, dry to constant weight.
2. methyl difluoroacetate Hydrogenation according to claim 1 is for the preparation method of the catalyst of difluoroethanol, it is characterized in that, in step one, aqueous slkali is NaOH or potassium hydroxide solution.
3. methyl difluoroacetate Hydrogenation according to claim 1 is for the preparation method of the catalyst of difluoroethanol, it is characterized in that, step 2 mesolite Powder Particle Size is 500-800 μm.
4. methyl difluoroacetate Hydrogenation according to claim 1 is for the preparation method of the catalyst of difluoroethanol, it is characterized in that, in step one, the granularity of vanadic anhydride is 100-300 μm.
5. methyl difluoroacetate Hydrogenation according to claim 1 is for the preparation method of the catalyst of difluoroethanol, it is characterized in that, in step 2, the granularity of artificial schellite is 100-300 μm.
6. methyl difluoroacetate Hydrogenation according to claim 1 is for the preparation method of the catalyst of difluoroethanol, it is characterized in that, in step 2, liquor potassic permanganate concentration is 5-10%.
7. methyl difluoroacetate Hydrogenation according to claim 1 is for the preparation method of the catalyst of difluoroethanol, it is characterized in that, in step 2, sintering time is 3-5 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110624584A (en) * | 2019-09-09 | 2019-12-31 | 浙江工业大学 | Fe-Zn-based nitrogen-doped nano catalyst and application thereof in preparation of fluoroalcohol compound |
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| CN102408304A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing alcohols by selectively hydrogenating aldehydes |
| CN103524306A (en) * | 2013-08-16 | 2014-01-22 | 巨化集团技术中心 | Method for preparing difluoroethanol by gas phase catalytic hydrogenation |
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| JP2797464B2 (en) * | 1989-04-14 | 1998-09-17 | 三菱化学株式会社 | Method for hydrogenating carbonyl compounds |
| CN102307657A (en) * | 2009-10-26 | 2012-01-04 | 国际人造丝公司 | Process for making ethanol from acetic acid using acidic catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110624584A (en) * | 2019-09-09 | 2019-12-31 | 浙江工业大学 | Fe-Zn-based nitrogen-doped nano catalyst and application thereof in preparation of fluoroalcohol compound |
| CN110624584B (en) * | 2019-09-09 | 2022-09-13 | 浙江工业大学 | Fe-Zn-based nitrogen-doped nano catalyst and application thereof in preparation of fluoroalcohol compound |
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Effective date of registration: 20190719 Address after: No. 31 Guangxing Road, Guangrao Economic Development Zone, Guangrao County, Dongying City, Shandong Province Patentee after: GREEN CHEMICAL (DONGYING) CO., LTD. Address before: 257 300 West of Yuehe Road and North of Guangxing Road, Guangrao County Economic Development Zone, Dongying City, Shandong Province Patentee before: DONGYING HAINA NEW MATERIAL CO., LTD. |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of catalyst for preparing difluoroethanol by hydrogenation of methyl difluoroacetate Effective date of registration: 20211223 Granted publication date: 20160817 Pledgee: Guangrao sub branch of Dongying Bank Co., Ltd Pledgor: GREEN CHEMICAL (DONGYING) Co.,Ltd. Registration number: Y2021980015782 |