CN100575339C - The method of amorphous alloy nickel catalysis m-(beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline - Google Patents
The method of amorphous alloy nickel catalysis m-(beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline Download PDFInfo
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- CN100575339C CN100575339C CN200710011807A CN200710011807A CN100575339C CN 100575339 C CN100575339 C CN 100575339C CN 200710011807 A CN200710011807 A CN 200710011807A CN 200710011807 A CN200710011807 A CN 200710011807A CN 100575339 C CN100575339 C CN 100575339C
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- hydroxyethyl sulfuryl
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- ASASRSMRAPYLQI-UHFFFAOYSA-N 2-(3-aminophenyl)sulfonylethanol Chemical compound NC1=CC=CC(S(=O)(=O)CCO)=C1 ASASRSMRAPYLQI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 10
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- -1 beta-hydroxyethyl sulfuryl Chemical group 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010974 bronze Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000003245 working effect Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 238000004904 shortening Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000809 Alumel Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the method for amorphous alloy nickel catalysis m-(beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline.This method as catalyzer, under relatively mild reaction conditions, adopts two-stage hydrogenation technology to finish step by step with amorphous alloy nickel.This method has overcome that traditional iron powder method yield is low, energy consumption is high, the shortcoming of contaminate environment, has more solved catalyzer short problem in work-ing life in the catalytic hydrogenation process process.Adopt method provided by the invention that m-(beta-hydroxyethyl sulfuryl) oil of mirbane is carried out hydrogenation reaction, not only improved reaction efficiency, shortened the reaction times, and prolonged the work-ing life of catalyzer.
Description
Technical field
The invention belongs to the applied technical field of a kind of non-crystalline state Ni-Al alloy catalyst in the dyestuff intermediate hydrogenation.Relate to the application of the modified amorphous alumel hydrogenation catalyst of a class, such catalyzer has good anti-poisoning capability, can be to m-(beta-hydroxyethyl sulfuryl) oil of mirbane shortening system m-(beta-hydroxyethyl sulfuryl) aniline.By adopting this catalyzer, improved reaction efficiency, shortened the reaction times, prolonged the work-ing life of catalyzer.
Background technology
Virtue nitro-compound reduction system aryl primary amine process not only is widely used in the manufacturing of dye well medicine intermediate. also be used for other organic synthesis industrial production.M-(beta-hydroxyethyl sulfuryl) aniline is the important intermediate of vinyl-sulfone reactive dyes, is generally prepared with iron powder or catalytic hydrogenating reduction by m-(beta-hydroxyethyl sulfuryl) oil of mirbane.The domestic iron powder reducing method that generally adopts in the electrolyte solution of this process, its disadvantage is to generate iron mud and the waste water that contains arylamine in a large number, causes severe contamination.Be the friendly type technology of development environment, people attempt to substitute original technology with shortening.The key of shortening is to develop the catalyzer of excellent property.And hydrogenation catalyst commonly used has precious metals pt, Pd, and Rh, Ir, Os, Ru, Re and non-noble metal Ni, Cu, Mo, Cr, Fe etc., wherein noble metal catalyst has activity and selectivity preferably to fragrant nitro-compound hydrogenation, can carry out hydrogenation at atmospheric or low pressure.Price with Pd in the precious metal is relatively low, and Pd/C is difficult for spontaneous combustion in the ordinary course of things, and is easy to operate and safe, and is widely used.Technological difficulties are that catalyst life is not long, and for noble metal catalyst, because price reasons, the durability issues of catalyzer generally receives domestic and international investigator's concern.The research of m-(beta-hydroxyethyl sulfuryl) oil of mirbane shortening system m-(beta-hydroxyethyl sulfuryl) aniline on the existing report skeletal nickel catalyst, but because the skeletal nickel catalyst inactivation is very fast in actual production, life-span is shorter, production cost is higher, thereby has influenced the further popularization of this catalyzer in industrial production.
Summary of the invention
The method that the purpose of this invention is to provide amorphous alloy nickel catalysis m-(beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline, its technical problem to be solved is after adopting this hydrogenation catalyst, and the easy row of the production technique operational safety of hydrogenation reaction has also been saved production cost.
Technical scheme of the present invention is: a kind of non-crystalline state modified raney ni catalysis m-(beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene prepares the method for m-(beta-hydroxyethyl sulfuryl) aniline, reaction conditions is: temperature of reaction is 50~90 ℃, reaction pressure is 0.5~1.2MPa, reaction times is 4~8h, and the mass ratio of catalyzer and raw material is 0.5~2.5.Described catalyzer is for being presoma with amorphous nickel aluminum alloy thin bar, and through the non-crystalline state modified skeletal nickel catalyst of alkali activation back preparation, its composition and preparation method are:
A. the major constituent as the thin bar of the amorphous alloy of catalyzer precursor is nickel and aluminium, and the interpolation component is M, and integral body is expressed as NiAlM, wherein adds component M and be one or more the mixing among Fe, Mn, Mo, W, Co, Cu or the Cr;
B. the preparation method of catalyst precursor non-crystalline state NiAlM alloy is: solid Ni, Al, M are warmed up to 1000-1600 ℃ according to the ratio of mass percent Ni 40-60%, Al 40-60%, M 0-20% under argon shield, make its fusing form the uniform alloy liquation, the fused alloy uses the cooling bronze drum quenching of high speed rotating to 30-80 ℃ in argon gas atmosphere, form the thin bar of amorphous alloy, become fine particle with ball mill grinding then, the catalyst fines of selecting the different grain size scope with sub-sieve is standby, and normally used size range is 20-100 μ m;
C. the activation method of catalyst precursor alloy NiAlM is: powdered alloy is slowly joined in the NaOH solution of 10-25wt%, launch to remove in 45-120 minute Al down at 70-100 ℃, wash to solution with deoxidation deionized water repeated multiple times and to be neutral, form the Ni-based hydrogenation catalyst of highly active non-crystalline state modified skeletal.
The mass ratio of first-selected catalyzer and raw material is 1.0~2.0, and temperature of reaction is 60~70 ℃, and reaction pressure is 0.8~1.0Mpa, and the reaction times is 5~6h.
Reaction equation of the present invention is:
The invention has the beneficial effects as follows:
1, adopts cheap amorphous nickel alloy catalyst to make m-(beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene catalyzer, have with precious metal palladium and make the close reactive behavior of catalyzer, greatly reduce the production cost of m-(beta-hydroxyethyl sulfuryl) aniline.
2, adopt the technology of amorphous nickel alloy catalyst catalysis m-(beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline, solved short problem of traditional technology skeletal nickel catalyst life-span, prolong the work-ing life of catalyzer, reduced production cost.
Embodiment
The present invention is further illustrated below in conjunction with embodiment
Embodiment 1
With 12g m-(beta-hydroxyethyl sulfuryl) oil of mirbane, 18ml methyl alcohol, 0.3g the non-crystalline state modified skeletal nickel catalyst joins in the vacant 75ml still formula high-pressure reactor together, respectively replace three times with nitrogen hydrogen airtight back, it is constant that the adjustment hydrogen valve makes system pressure keep the 0.8MPa maintenance, reacts 5h down at 60 ℃.Sampling analysis, the transformation efficiency of m-(beta-hydroxyethyl sulfuryl) oil of mirbane is 100%, the yield of m-(beta-hydroxyethyl sulfuryl) aniline is 98.5%.
Embodiment 2
With 12g m-(beta-hydroxyethyl sulfuryl) oil of mirbane, 30ml methyl alcohol, 0.3g the non-crystalline state modified skeletal nickel catalyst joins in the vacant 75ml still formula high-pressure reactor together, respectively replace three times with nitrogen hydrogen airtight back, it is constant that the adjustment hydrogen valve makes system pressure keep the 1.0MPa maintenance, reacts 4.5h down at 70 ℃.Sampling analysis, the transformation efficiency of m-(beta-hydroxyethyl sulfuryl) oil of mirbane is 100%, the yield of m-(beta-hydroxyethyl sulfuryl) aniline is 98.8%.
Embodiment 3
With 24g m-(beta-hydroxyethyl sulfuryl) oil of mirbane, 36ml methyl alcohol, 0.5g the non-crystalline state modified skeletal nickel catalyst joins in the vacant 100ml still formula high-pressure reactor together, respectively replace three times with nitrogen hydrogen airtight back, it is constant that the adjustment hydrogen valve makes system pressure keep the 1.0MPa maintenance, reacts 4h down at 70 ℃.Sampling analysis, the transformation efficiency of m-(beta-hydroxyethyl sulfuryl) oil of mirbane is 100%, the yield of m-(beta-hydroxyethyl sulfuryl) aniline is 98.3%.
Embodiment 4
With 48g m-(beta-hydroxyethyl sulfuryl) oil of mirbane, 72ml methyl alcohol, 1.0g the non-crystalline state modified skeletal nickel catalyst joins in the vacant 200ml still formula high-pressure reactor together, respectively replace three times with nitrogen hydrogen airtight back, it is constant that the adjustment hydrogen valve makes system pressure keep the 1.0MPa maintenance, reacts 5h down at 70 ℃.Sampling analysis, the transformation efficiency of m-(beta-hydroxyethyl sulfuryl) oil of mirbane is 100%, the yield of m-(beta-hydroxyethyl sulfuryl) aniline is 98.6%.
Embodiment 5
With 120g m-(beta-hydroxyethyl sulfuryl) oil of mirbane, 180ml methyl alcohol, 1.8g the non-crystalline state modified skeletal nickel catalyst joins in the vacant 500ml still formula high-pressure reactor together, respectively replace three times with nitrogen hydrogen airtight back, it is constant that the adjustment hydrogen valve makes system pressure keep the 1.0MPa maintenance, reacts 5h down at 70 ℃.Sampling analysis, the transformation efficiency of m-(beta-hydroxyethyl sulfuryl) oil of mirbane is 100%, the yield of m-(beta-hydroxyethyl sulfuryl) aniline is 98.8%.
Embodiment 6
With 150g m-(beta-hydroxyethyl sulfuryl) oil of mirbane, 225ml methyl alcohol, 2g non-crystalline state modified skeletal nickel catalyst joins in the vacant 75ml still formula high-pressure reactor together, respectively replace three times with nitrogen hydrogen airtight back, it is constant that the adjustment hydrogen valve makes system pressure keep the 1.0MPa maintenance, reacts 5h down at 70 ℃.Sampling analysis, the transformation efficiency of m-(beta-hydroxyethyl sulfuryl) oil of mirbane is 100%, the yield of m-(beta-hydroxyethyl sulfuryl) aniline is 98.7%.
Claims (5)
1, the method for a kind of non-crystalline state modified raney ni catalysis m-(beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline, it is characterized in that, reaction conditions is: temperature of reaction is 50~90 ℃, reaction pressure is 0.5~1.2MPa, reaction times is 4~8h, and the mass ratio of catalyzer and raw material is 0.5~2.5, and catalyzer is for being presoma with amorphous nickel aluminum alloy thin bar, the non-crystalline state modified skeletal nickel catalyst of preparation after the alkali activation, it is formed and the preparation method is:
A. the major constituent as the thin bar of the amorphous alloy of catalyzer precursor is nickel and aluminium, and the interpolation component is M, and integral body is expressed as NiAlM, wherein adds component M and be one or more the mixing among Fe, Mn, Mo, W, Co, Cu or the Cr;
B. the preparation method of catalyst precursor non-crystalline state NiAlM alloy is: solid Ni, Al, M are warmed up to 1000-1600 ℃ according to the ratio of mass percent Ni 40-60%, Al 40-60%, M 0-20% under argon shield, make its fusing form the uniform alloy liquation, the fused alloy uses the cooling bronze drum quenching of high speed rotating to 30-80 ℃ in argon gas atmosphere, form the thin bar of amorphous alloy, become fine particle with ball mill grinding then, the catalyst fines of selecting the different grain size scope with sub-sieve is standby, and normally used size range is 20-100 μ m;
C. the activation method of catalyst precursor alloy NiAlM is: powdered alloy is slowly joined in the NaOH solution of 10-25wt%, launch to remove in 45-120 minute Al down at 70-100 ℃, wash to solution with deoxidation deionized water repeated multiple times and to be neutral, form the Ni-based hydrogenation catalyst of highly active non-crystalline state modified skeletal.
2, the method for non-crystalline state modified raney ni catalysis m-according to claim 1 (beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline is characterized in that, the mass ratio of described catalyzer and raw material is 1.0~2.0.
3, the method for non-crystalline state modified raney ni catalysis m-according to claim 1 (beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline is characterized in that, described temperature of reaction is 60~70 ℃.
4, the method for non-crystalline state modified raney ni catalysis m-according to claim 1 (beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline is characterized in that, described reaction pressure is 0.8~1.0MPa.
5, the method for non-crystalline state modified raney ni catalysis m-according to claim 1 (beta-hydroxyethyl sulfuryl) hydrogenation of chloronitrobenzene system m-(beta-hydroxyethyl sulfuryl) aniline is characterized in that, the described reaction times is 5~6h.
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CN102304053A (en) * | 2011-07-22 | 2012-01-04 | 湖南化工研究院 | Preparation method for synthesizing naphthylamine by catalytic hydrogenation |
CN102728363B (en) * | 2012-06-04 | 2014-05-28 | 赛鼎工程有限公司 | Preparation method of urushibara nickel catalyst |
CN102744071B (en) * | 2012-06-04 | 2014-07-30 | 赛鼎工程有限公司 | Supported urushibara nickel catalyst |
CN102744083B (en) * | 2012-06-26 | 2015-11-18 | 华烁科技股份有限公司 | The preparation of the special Raney's nickel-aluminium-X catalyst of Isosorbide-5-Nitrae-butynediols Hydrogenation BDO and activation method |
CN103302257A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Preparation method of aniline hydrogenating amorphous nickel-aluminum catalyst |
CN103467347B (en) * | 2013-08-30 | 2015-07-08 | 江苏和利瑞科技发展有限公司 | Preparation method of m-(beta-hydroxy ethyl sulfuryl) aniline |
CN105749972B (en) * | 2014-12-17 | 2018-11-02 | 中国科学院大连化学物理研究所 | A kind of hydrogenation of petroleum resin catalyst and its preparation method and application |
CN106475099B (en) * | 2016-08-31 | 2018-12-18 | 杭州绿一环保技术有限公司 | A kind of preparation method of the highly active Fe catalyst of low cost |
CN106518736A (en) * | 2016-10-11 | 2017-03-22 | 浙江劲光实业股份有限公司 | Preparation method of 4-(beta-hydroxyethyl sulfone sulfate)-1,3-phenylenediamine and degreased product thereof |
CN106925293B (en) * | 2017-03-28 | 2020-03-31 | 上海迅凯新材料科技有限公司 | Nickel-based catalyst and preparation method and application thereof |
CN108003073A (en) * | 2017-12-21 | 2018-05-08 | 广东众和化塑有限公司 | The preparation method of amino-phenyl-beta-hydroxyethyl sulfone and p-aminophenyl-beta-hydroxyethyl sulfone sulphonic acid ester |
CN112958114A (en) * | 2021-02-09 | 2021-06-15 | 大连理工大学 | Raney nickel catalyst for hydrogenation of aromatic nitro compound in fixed bed and application thereof |
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