CN101745396A - Catalyst for preparing succinic acid dialkyl ester and preparation method thereof - Google Patents
Catalyst for preparing succinic acid dialkyl ester and preparation method thereof Download PDFInfo
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- CN101745396A CN101745396A CN 200810238879 CN200810238879A CN101745396A CN 101745396 A CN101745396 A CN 101745396A CN 200810238879 CN200810238879 CN 200810238879 CN 200810238879 A CN200810238879 A CN 200810238879A CN 101745396 A CN101745396 A CN 101745396A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 150000002148 esters Chemical class 0.000 title claims abstract description 19
- 239000001384 succinic acid Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- -1 alkyl maleate Chemical compound 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 206010013786 Dry skin Diseases 0.000 claims description 8
- 229960004643 cupric oxide Drugs 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000008367 deionised water Substances 0.000 abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000005751 Copper oxide Substances 0.000 abstract 2
- 229910000431 copper oxide Inorganic materials 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- 229960002097 dibutylsuccinate Drugs 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for alkyl maleate hydrogenation preparing succinic acid dialkyl ester and a preparation method thereof. The catalyst is composed of a main active component and auxiliary agents, wherein the main active component is copper oxide, and the auxiliary agents are aluminium oxide and zinc oxide. In the total weight of the catalyst, the copper oxide accounts for 40-60%, the zinc oxide accounts for 20-50%, and the aluminium oxide accounts for 10-20%. The preparation method comprises the following steps: dissolving soluble salts in the main active component and the auxiliary agents in deionized water, neutralizing by an alkali solution in heat stirring until pH is equal to 7, precipitation filtering the generated product, washing, drying, calcination and molding. The catalyst is used for alkyl maleate hydrogenation preparing 1,4-succinic acid dialkyl ester, which can realize lower reaction pressure, therefore greatly reducing the one-time investment and production cost of a production device.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for the alkyl maleate hydrogenation preparing succinic acid dialkyl ester.
Background technology
Succinic acid dialkyl ester is commonly used for solvent, organic synthesis intermediate, food additives, gas-chromatography fixer etc.The synthetic method of industrial routine is to be formed by succinic acid and corresponding pure esterification under sulphuric acid catalysis, the highly acid of sulfuric acid, severe corrosive, easily causes that side reaction (as charing, oxidation, polymerization etc.) and environmental pollution are the problems that current chemical industry is needed solution badly.
Though disclosed in CN 200610117295.6, CN1049208C, CN 99113206.8 and these patents of US4584419 is with dialkyl maleate and/or succinic acid dialkyl ester raw material gas phase hydrogenation preparation 1, the method of 4-butanediol, but all relate to the reaction that dibutyl maleate is converted into dibutyl succinate in the reaction mechanism of these methods.
Summary of the invention
The purpose of this invention is to provide a kind of Catalysts and its preparation method that is used for the alkyl maleate hydrogenation preparing succinic acid dialkyl ester, making its hydrogenation produce succinic acid dialkyl ester can realize under lower reaction pressure, reduce process units one-time investment and production cost, realize easy to operate.
Catalyst of the present invention is base metal and the hydrogenation catalyst that does not contain the chromium component, specifically, the catalyst that is used for the alkyl maleate hydrogenation preparing succinic acid dialkyl ester provided by the invention, form by main active component and auxiliary agent, main active component is a cupric oxide, and auxiliary agent is aluminium oxide and zinc oxide; Cupric oxide accounts for 40~60% of total catalyst weight, and zinc oxide accounts for 20~50% of total catalyst weight, and aluminium oxide accounts for 10~20% of total catalyst weight.
The present invention prepares the method for above-mentioned catalyst, and its key step is:
The soluble-salt of copper, zinc, aluminium is mixed back water dissolving in proportion, make mixed solution, under the heating stirring condition, the pH that regulates this miscible fluid with precipitating reagent is 6~8;
With the precipitation that generates filter, wash, 100~150 ℃ of dryings 4~12 hours, 350~450 ℃ of roastings 3~6 hours prepare catalyst;
In the catalyst for preparing, cupric oxide accounts for 40~60% of total catalyst weight, and zinc oxide accounts for 20~50% of total catalyst weight, and aluminium oxide accounts for 10~20% of total catalyst weight.
Among the preparation method of the present invention, the soluble-salt of copper, zinc, aluminium is its nitrate, chloride, acetic acid, oxalates or other soluble-salts, and precipitating reagent is NaOH, sodium carbonate, ammoniacal liquor or oxalic acid.
To above-mentioned made catalyst, must in 300 ℃ hydrogen stream, reduce 3~6 hours before using.
According to CuZnAl catalyst provided by the invention, after treatment, has higher specific surface area.This catalyst shows good hydrogenation activity and selectivity in the reaction of alkyl maleate hydrogenation preparing succinic acid dialkyl ester after reducing, catalytic performance is stable in 1000 hours life assessments.
The used raw material dialkyl maleate of hydrogen is C
1~C
5Arrcostab, preferred especially n-butyl.
In miniature continuous fixed bed reactors, investigate catalyst activity.Catalyst powder granulation to 20 after the roasting~40 orders, the microreactor reaction tube of packing into (internal diameter 8mm) is with the pure hydrogen reduction activation.Dialkyl maleate is squeezed in the reactor through duplex plunger pump, pressurizes then, heats up, reacts.
The present invention compared with prior art, its significant effect is: with the ternary component catalyst of forming with auxiliary agent zinc oxide, aluminium oxide based on the active component cupric oxide provided by the invention, being used for the dibutyl maleate is that raw material carries out catalytic hydrogenation, the preparation dibutyl succinate.
The specific embodiment
Below in conjunction with embodiment method of the present invention being described further, is not limitation of the invention.
Embodiment 1:
60.73g copper nitrate (Cu (NO
3)
23H
2O), 74.91g zinc nitrate (Zn (NO
3)
26H
2O) and 19.8g aluminum nitrate (Al (NO
3)
29H
2O) be dissolved in the 800ml deionized water.Adding under the thermal agitation, with the aqueous slkali NaOH pH=7 that neutralizes, the precipitation of generation after filtration, after the washing, 120 ℃ of dryings 5 hours, in 400 ℃ of roastings 4 hours, moulding.Before catalyst used, reduction was 4 hours in 300 ℃ of hydrogen streams.Dialkyl maleate is squeezed in the reactor through duplex plunger pump, pressurizes then, heats up, reacts.100 ± 1 ℃ of hydroconversion reaction zone reaction temperatures, 5MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result sees Table 1.
Embodiment 2:
32.98g copper nitrate (Cu (NO
3)
23H
2O), 74.53g zinc nitrate (Zn (NO
3)
26H
2O) and 14.75g aluminum nitrate (Al (NO
3)
29H
2O) be dissolved in the 800ml deionized water.Adding under the thermal agitation, with the aqueous slkali sodium carbonate pH=7 that neutralizes, the precipitation of generation after filtration, after the washing, 120 ℃ of dryings 5 hours, in 400 ℃ of roastings 4 hours, moulding.Before catalyst used, reduction was 4 hours in 300 ℃ of hydrogen streams.Dialkyl maleate is squeezed in the reactor through duplex plunger pump, pressurizes then, heats up, reacts.100 ± 1 ℃ of hydroconversion reaction zone reaction temperatures, 5MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result sees Table 1.
Embodiment 3:
60.66g copper nitrate (Cu (NO
3)
23H
2O), 37.39g zinc nitrate (Zn (NO
3)
26H
2O) and 14.86g aluminum nitrate (Al (NO
3)
29H
2O) be dissolved in the 800ml deionized water.Adding under the thermal agitation, with the aqueous slkali ammoniacal liquor pH=7 that neutralizes, the precipitation of generation after filtration, after the washing, 120 ℃ of dryings 5 hours, in 400 ℃ of roastings 4 hours, moulding.Before catalyst used, reduction was 4 hours in 300 ℃ of hydrogen streams.Dialkyl maleate is squeezed in the reactor through duplex plunger pump, pressurizes then, heats up, reacts.100 ± 1 ℃ of hydroconversion reaction zone reaction temperatures, 5MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result sees Table 1.
Embodiment 4:
32.98g copper nitrate (Cu (NO
3)
23H
2O), 74.53g zinc nitrate (Zn (NO
3)
26H
2O) and 14.75g aluminum nitrate (Al (NO
3)
29H
2O) be dissolved in the 800ml deionized water.Adding under the thermal agitation, with the aqueous slkali sodium carbonate pH=7 that neutralizes, the precipitation of generation after filtration, after the washing, 120 ℃ of dryings 5 hours, in 350 ℃ of roastings 4 hours, moulding.Before catalyst used, reduction was 4 hours in 300 ℃ of hydrogen streams.Dialkyl maleate is squeezed in the reactor through duplex plunger pump, pressurizes then, heats up, reacts.100 ± 1 ℃ of hydroconversion reaction zone reaction temperatures, 5MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result sees Table 1.
Embodiment 5:
32.98g copper nitrate (Cu (NO
3)
23H
2O), 74.53g zinc nitrate (Zn (NO
3)
26H
2O) and 14.75g aluminum nitrate (Al (NO
3)
29H
2O) be dissolved in the 800ml deionized water.Adding under the thermal agitation, with the aqueous slkali sodium carbonate pH=7 that neutralizes, the precipitation of generation after filtration, after the washing, 120 ℃ of dryings 5 hours, in 600 ℃ of roastings 4 hours, moulding.Before catalyst used, reduction was 4 hours in 300 ℃ of hydrogen streams.Dialkyl maleate is squeezed in the reactor through duplex plunger pump, pressurizes then, heats up, reacts.100 ± 1 ℃ of hydroconversion reaction zone reaction temperatures, 5MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result sees Table 1.
Embodiment 6:
32.98g copper nitrate (Cu (NO
3)
23H
2O), 74.53g zinc nitrate (Zn (NO
3)
26H
2O) and 14.75g aluminum nitrate (Al (NO
3)
29H
2O) be dissolved in the 800ml deionized water.Adding under the thermal agitation, with the aqueous slkali sodium carbonate pH=7 that neutralizes, the precipitation of generation after filtration, after the washing, 120 ℃ of dryings 5 hours, in 800 ℃ of roastings 4 hours, moulding.Before catalyst used, reduction was 4 hours in 300 ℃ of hydrogen streams.Dialkyl maleate is squeezed in the reactor through duplex plunger pump, pressurizes then, heats up, reacts.100 ± 1 ℃ of hydroconversion reaction zone reaction temperatures, 5MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result sees Table 1.
Table 1: the catalyst result of alkyl maleate hydrogenation preparing succinic acid dialkyl ester gathers
According to the result of the foregoing description, illustrate that the temperature of its operation process conditions, pressure are starkly lower than prior art.So manufacturing condition will inevitably reduce the pressure requirement to consersion unit, thereby also can reduce the one-time investment and the production cost of reaction unit largely, also can reduce operation easier.
Claims (5)
1. catalyst that is used for the alkyl maleate hydrogenation preparing succinic acid dialkyl ester, it is characterized in that: catalyst is made up of main active component and auxiliary agent, and main active component is a cupric oxide, and auxiliary agent is aluminium oxide and zinc oxide; Cupric oxide accounts for 40~60% of total catalyst weight, and zinc oxide accounts for 20~50% of total catalyst weight, and aluminium oxide accounts for 10~20% of total catalyst weight.
2. the described Preparation of catalysts method of claim 1, its key step is:
The soluble-salt of copper, zinc, aluminium is mixed back water dissolving in proportion, make mixed solution, under the heating stirring condition, the pH that regulates this miscible fluid with precipitating reagent is 6~8;
With the precipitation that generates filter, wash, 100~150 ℃ of dryings 4~12 hours, 350~450 ℃ of roastings 3~6 hours prepare catalyst;
In the catalyst for preparing, cupric oxide accounts for 40~60% of total catalyst weight, and zinc oxide accounts for 20~50% of total catalyst weight, and aluminium oxide accounts for 10~20% of total catalyst weight.
3. preparation method according to claim 2, wherein, the soluble-salt of copper, zinc, aluminium is respectively its nitrate, chloride, acetic acid or oxalates; Precipitating reagent is NaOH, sodium carbonate, ammoniacal liquor or oxalic acid.
4. according to the described preparation method of claim 2, wherein, baking temperature is 120 ℃, and be 5 hours drying time, and sintering temperature is 400 ℃, and roasting time is 4 hours.
5. according to the described preparation method of claim 2, wherein, the catalyst for preparing reduced 3~6 hours in 280~300 ℃ of hydrogen streams before use.
Priority Applications (1)
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CN 200810238879 CN101745396B (en) | 2008-12-03 | 2008-12-03 | Catalyst for preparing succinic acid dialkyl ester and preparation method thereof |
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CN101745396A true CN101745396A (en) | 2010-06-23 |
CN101745396B CN101745396B (en) | 2013-05-01 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101979139A (en) * | 2010-10-26 | 2011-02-23 | 中国科学院山西煤炭化学研究所 | Catalyst of succinic acid dicarboxylic ester and preparation method thereof |
CN102001939A (en) * | 2010-10-26 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Method for preparing succinate |
CN102600836A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院新疆理化技术研究所 | Preparation method and application of catalyst for synthesizing dialkyl succinate |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1164548C (en) * | 2001-04-13 | 2004-09-01 | 中国石化集团天津石油化工公司 | Catalyst for hydrogenating 1,4-dimethyl hexahydroterephthalate to produce 1,4-dimethyl cyclohexanol and its prepn process |
CN1565728A (en) * | 2003-06-18 | 2005-01-19 | 中国石油天然气股份有限公司 | Catalyst and method for preparing 1, 5-pentanediol by hydrogenating dimethyl 1, 5-glutarate |
-
2008
- 2008-12-03 CN CN 200810238879 patent/CN101745396B/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101979139A (en) * | 2010-10-26 | 2011-02-23 | 中国科学院山西煤炭化学研究所 | Catalyst of succinic acid dicarboxylic ester and preparation method thereof |
CN102001939A (en) * | 2010-10-26 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Method for preparing succinate |
CN101979139B (en) * | 2010-10-26 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst of succinic acid dicarboxylic ester and preparation method thereof |
CN102001939B (en) * | 2010-10-26 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Method for preparing succinate |
CN102600836A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院新疆理化技术研究所 | Preparation method and application of catalyst for synthesizing dialkyl succinate |
CN102600836B (en) * | 2012-02-09 | 2014-03-19 | 中国科学院新疆理化技术研究所 | Preparation method and application of catalyst for synthesizing dialkyl succinate |
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