CN102527393A - Modification method for raney nickel catalyst for p-chloronitrobenzene hydrogenation - Google Patents

Modification method for raney nickel catalyst for p-chloronitrobenzene hydrogenation Download PDF

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Publication number
CN102527393A
CN102527393A CN2011104379920A CN201110437992A CN102527393A CN 102527393 A CN102527393 A CN 102527393A CN 2011104379920 A CN2011104379920 A CN 2011104379920A CN 201110437992 A CN201110437992 A CN 201110437992A CN 102527393 A CN102527393 A CN 102527393A
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China
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nickel catalyst
minutes
hydrogenation
skeletal nickel
catalyst
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CN2011104379920A
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孙盛凯
李玉杰
金汉强
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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Abstract

The invention relates to a modification method for a raney nickel catalyst for p-chloronitrobenzene hydrogenation, and belongs to the technical field of organic synthesis. According to the method, a catalyst is added to deionized water containing 1-5% of a modifier, a stirring reaction is performed for 20-40 minutes at a temperature of 30-70 DEG C, and a standing treatment is performed for 30-90 minutes; a reduction agent with the concentration of 5-15% is added, a stirring reaction is performed for 30-60 minutes at the temperature of 40-50 DEG C, and NaHCO3 is adopted to adjust the pH value to 8-10, wherein a mass ratio of the reduction agent to the raney nickel catalyst is 4:1-8:1; a standing treatment is performed for 30-60 minutes, and deionized water is adopted to wash until the solution is neutral, a filtering treatment is performed, water is added, and sealed preservation is performed to prepare the modified raney nickel catalyst. According to the present invention, under the condition of no addition of the dechlorination inhibitor, the p-chloronitrobenzene conversion rate is more than or equal to 99.9%, the dechlorination side reaction generation rate in the p-chloronitrobenzene hydrogenation process is less than or equal to 2%, and the yield of p-chloroaniline is more than or equal to 95%; compared to the existing methods for preparing the hydrogenation catalyst, the method of the present invention has the following advantages that: the hydrogenation process is simplified, the three waste is less after the hydrogenation, the cost is low, the energy consumption is low, and the industrial requirements of quality increasing, consumption reducing, and environmental protection are achieved.

Description

A kind of parachloronitrobenzene hydrogenation is with the method for modifying of skeletal nickel catalyst
Technical field
The invention belongs to technical field of organic synthesis, propose the parachloronitrobenzene hydrogenation is carried out modification, modification with skeletal nickel catalyst method.
Background technology
Nickel (Raney Ni) is that a kind of extremely important hydrogenation is used catalyst, and it is widely used in hydrogenation process, as is applied to the hydrogenation of alkynes, alkene, aryl, carbonyl, nitro and itrile group, and use amount is also bigger.The catalytic reaction process of Raney nickel roughly was divided into for four steps: (1) hydrogen is in the absorption of metallic nickel particle surface and split into hydrogen atom; (2) absorption of reactant; (3) surface reaction; (4) product desorption.Therefore in adding the hydrogenation process, directly have influence on quality, yield and the economic benefit of product in the activity of Raney's nickel catalyst and service life.Along with the raising of catalysis industry to the catalyst performance requirement; Raney's nickel is as a kind of traditional hydrogenation catalyst; Its limitation showing gradually; Mainly be that a large amount of micropores that occur when some remaining impurity and catalyst are handled with caustic alkali become the principal element that influences reaction selectivity because skeleton nickel is in preparing processing procedure; And the hear resistance of this catalyst is also relatively poor, is prone to form hot-spot, has limited its production capacity and life of catalyst.Therefore, when the existing commercial production of improvement is with Raney's nickel catalyst, also should develop high activity, high selectivity, high stability and eco-friendly novel catalyst.
The modification of skeletal nickel catalyst is present research emphasis direction; The modification of catalyst can not reduce under the catalyst activity prerequisite; Can modify skeletal nickel catalyst according to the demand to catalytic activity in the hydrogenation process; Make its hydrogenation activity can adapt to the catalytic reaction requirement better, avoid adding in the hydrogenation process all the other cocatalysts.Thereby reach the purpose that improves conversion ratio, reduction rate of side effects, improves product yield.In commercial Application, can simplify product treatment technology behind the hydrogenation, cut down the consumption of energy, reduce environmental pollution through the skeletal nickel catalyst of modification.
From the gas phase permeation precipitation method for preparation patents such as (CN1806920) of the preparation of existing patent of invention such as a kind of catalyst of phosphatizing nickel and preparation method and application (CN 101376108A), supported nanometer nickel catalyst and application (CN 101143323A) thereof, a kind of supported nanometer nickel hydrogenation catalyst, the domestic research overwhelming majority to skeletal nickel catalyst all concentrates on the early stage of skeletal nickel catalyst among the preparation technology.And it is less to the study on the modification of later stage skeletal nickel catalyst.And the requirement to skeletal nickel catalyst is had nothing in common with each other in organic chemical industry's hydrogenation technique, and this just makes skeletal nickel catalyst can not be applied even more extensively in various hydrogenation techniques.Reduced the market share.
And from external research to skeletal nickel catalyst, the interpolation noble metal carries out study on the modification to skeletal nickel catalyst to be admitted by everybody.Therefore, on the basis of skeletal nickel catalyst preparation, add the emphasis direction that performance that stronger noble metal of various catalytic activitys and complementary metal improved skeletal nickel catalyst also becomes foreign study in right amount.Wherein, the noble metal of interpolation mainly contains palladium, platinum etc., and assistant metal is Zn, Cd, Cu and Ag etc.Under the prerequisite of present Pd/Ni bimetallic catalyst commercial Application, the study on the modification to the Pd/Ni bimetallic catalyst after the interpolation of assistant metal becomes main direction of studying.
Summary of the invention
The object of the invention mainly is the parachloronitrobenzene catalytic hydrogenation is carried out the modification and the modification in later stage with skeletal nickel catalyst, makes it more effectively carry out hydrogenation to paranitrochlorobenzene.
The present invention proposes the method for modifying of a kind of parachloronitrobenzene hydrogenation with skeletal nickel catalyst, it is characterized in that process is following: get skeletal nickel catalyst, adding consumption is the modified metal material of skeletal nickel catalyst mass fraction 1%～5%; 30 ℃～70 ℃ following stirring reactions 20 minutes-40 minutes; Left standstill 30～90 minutes, adding concentration again is 5%～15%, with the mass ratio of skeletal nickel catalyst be the reducing agent of 4:1～8:1; 30 ℃～70 ℃ are stirred reduction down, and use NaHCO 3Regulate pH value to 8～10,30～60 minutes reaction time, be washed till neutrality, add the water-stop preservation after filtering with deionized water, prepare modified skeletal nickel catalyst.
The catalyst modification thing that can supply select for use is a slaine, for reaction, and preferred slaine such as the Zn (NO in one or more following thing groups 3) 2, CuSO 4, (NH 4) 6Mo 7O 24, Fe 2(SO 4) 3, Al 2(SO 4) 3, Cr (NO 3) 39H 2O.Preferred again Zn (NO 3) 2, CuSO 4, (NH4) 6Mo 7O 24, Cr (NO 3) 39H 2O.Preferred (NH4) again 6Mo 7O 24, Cr (NO 3) 39H 2A kind of among the O.The consumption of metal object is 1%～5% of a skeletal nickel catalyst consumption; Preferred 2%～3%.
Can supply to select for use reducing agent is formaldehyde, hydrazine hydrate, phosphorous acid, ortho phosphorous acid, NaBH 4In one or more.Preferred ortho phosphorous acid, NaBH 4In a kind of.The reductant concentration of selecting for use is 5%～15%; Preferred 8%～12%.The mass ratio of reducing agent and catalyst is 4:1～8:1; Preferred 5:1～6:1.
Stirring, reduction temperature are 30 ℃～70 ℃; Preferred 40 ℃～50 ℃.
The present invention adds precious metal solution in skeleton nickel, through stirring the noble metal skeletal nickel catalyst for preparing after the reduction after the modification.Thereby avoided in the parachloronitrobenzene hydrogenation reaction, adding organic matter as the dechlorination inhibitor.Reduce subsequent treatment process, reduced cost.Under the prerequisite that parachloronitrobenzene 99.9% transforms, the selectivity of parachloroanilinum >=98%, yield >=95%.
The specific embodiment
Below in conjunction with embodiment the present invention is described in detail.
Embodiment 1
Get unmodified skeletal nickel catalyst 10g, add deionized water 30g, Zn (NO 3) 23g.Add in the 100ml beaker 50 ℃ of magnetic agitation 30 minutes, left standstill 60 minutes, add reducing agent ortho phosphorous acid solution 60g, magnetic agitation 45 minutes, and use NaHCO 3Regulating pH value is 9.Left standstill 45 minutes, washing obtains modified skeletal nickel catalyst to neutral after the filtration.
The parachloronitrobenzene hydrogenation is estimated: parachloronitrobenzene conversion ratio 96%, selectivity >=94%, yield >=92%.
Embodiment 2
Get unmodified skeletal nickel catalyst 10g, add deionized water 30g, CuSO 43g.Add in the 100ml beaker 50 ℃ of magnetic agitation 30 minutes, left standstill 60 minutes, add reducing agent ortho phosphorous acid solution 60g, magnetic agitation 45 minutes, and use NaHCO 3Regulating pH value is 9.Left standstill 45 minutes, washing obtains modified skeletal nickel catalyst to neutral after the filtration.
The parachloronitrobenzene hydrogenation is estimated: parachloronitrobenzene conversion ratio 98%, selectivity >=95%, yield >=93%.
Embodiment 3
Get unmodified skeletal nickel catalyst 10g, add deionized water 30g, Cr (NO 3) 33g.Add in the 100ml beaker 50 ℃ of magnetic agitation 30 minutes, left standstill 60 minutes, add reducing agent ortho phosphorous acid solution 60g, magnetic agitation 45 minutes, and use NaHCO 3Regulating pH value is 9.Left standstill 45 minutes, washing obtains modified skeletal nickel catalyst to neutral after the filtration.
The parachloronitrobenzene hydrogenation is estimated: parachloronitrobenzene conversion ratio 98%, selectivity >=93%, yield >=90%.
Embodiment 4
Get unmodified skeletal nickel catalyst 10g, add deionized water 30g, (NH4) 6Mo 7O 243g.Add in the 100ml beaker 50 ℃ of magnetic agitation 30 minutes, left standstill 60 minutes, add reducing agent ortho phosphorous acid solution 60g, magnetic agitation 45 minutes, and use NaHCO 3Regulating pH value is 9.Left standstill 45 minutes, washing obtains modified skeletal nickel catalyst to neutral after the filtration.
The parachloronitrobenzene hydrogenation is estimated: parachloronitrobenzene conversion ratio 99.9%, selectivity >=98%, yield >=95%.
Embodiment 5
Get unmodified skeletal nickel catalyst 10g, add deionized water 30g, Fe 2(SO 4) 33g.Add in the 100ml beaker 50 ℃ of magnetic agitation 30 minutes, left standstill 60 minutes, add reducing agent ortho phosphorous acid solution 60g, magnetic agitation 45 minutes, and use NaHCO 3Regulating pH value is 9.Left standstill 45 minutes, washing obtains modified skeletal nickel catalyst to neutral after the filtration.
The parachloronitrobenzene hydrogenation is estimated: parachloronitrobenzene conversion ratio 99%, selectivity >=95%, yield >=93%.
The present invention is not limited to the technology described in the embodiment, and its description is illustrative, is not limitation.

Claims (10)

1. a paranitrochlorobenzene hydrogenation is characterized in that with the method for modifying of skeletal nickel catalyst process is following: get skeletal nickel catalyst, add the modified metal material of skeletal nickel catalyst consumption mass fraction 1%～5%; 30 ℃～70 ℃ following stirring reactions 20 minutes-40 minutes; Left standstill 30～90 minutes, adding mass percentage concentration again is 5%～15%, with the mass ratio of skeletal nickel catalyst be the reducing agent of 4:1～8:1; 30 ℃～70 ℃ are stirred reduction down, and use NaHCO 3Regulate pH value to 8～10,30～60 minutes reaction time, be washed till neutrality, add the water-stop preservation after filtering with deionized water, prepare modified skeletal nickel catalyst.
2. method according to claim 1 is characterized in that the metallics that the skeletal nickel catalyst modification is added is a slaine.
3. method according to claim 2 is characterized in that metallics is that one or more are selected from the slaine in the following thing group: Zn (NO 3) 2, CuSO 4, (NH 4) 6Mo 7O 24, Fe 2(SO4) 3, Al 2(SO 4) 3, Cr (NO 3) 39H 2O.
4. method according to claim 3 is characterized in that metallics is Zn (NO 3) 2, CuSO 4, (NH 4) 6Mo 7O 24, Cr (NO 3) 39H 2Among the O one or more.
5. according to claim 3 or 4 described methods, it is characterized in that metallics is (NH 4) 6Mo 7O 24, Cr (NO 3) 39H 2O's is a kind of.
6. method according to claim 1 and 2, the consumption that it is characterized in that said metallics is 2%～3% of a skeletal nickel catalyst consumption.
7. method according to claim 1 is characterized in that described reducing agent is one or more among formaldehyde, hydrazine hydrate, phosphorous acid, ortho phosphorous acid, the NaBH4.
8. method according to claim 7 is characterized in that said reducing agent is ortho phosphorous acid, NaBH 4In a kind of.
9. according to claim 1 or 7 described methods, it is characterized in that the consumption of said reducing agent and the mass ratio of skeletal nickel catalyst are 5:1～6:1, reductant concentration is 8%～12%.
10. method according to claim 1 is characterized in that stirring, reduction temperature are 40 ℃～50 ℃.
CN2011104379920A 2011-12-23 2011-12-23 Modification method for raney nickel catalyst for p-chloronitrobenzene hydrogenation Pending CN102527393A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103497112A (en) * 2013-09-18 2014-01-08 葫芦岛天启晟业化工有限公司 Method for preparing p-chloroaniline without adding organic solvent
CN111302956A (en) * 2020-04-14 2020-06-19 国药集团化学试剂有限公司 Preparation method of 4-bromo-2-aminophenol

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1310053A (en) * 2000-02-24 2001-08-29 中国石油化工集团公司 Regeneration process of catalyst for preparing metaphylene dimethylamine
CN1974559A (en) * 2006-12-21 2007-06-06 天津大学 Skeleton nickel catalyzed 5-nitrobenzimidazole ketone reducing process for preparing 5-aminobenzimidazole ketone
CN101182295A (en) * 2007-12-14 2008-05-21 浙江工业大学 Method for synthesizing 2-amido-5-chlorobenzotrifluoride

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1310053A (en) * 2000-02-24 2001-08-29 中国石油化工集团公司 Regeneration process of catalyst for preparing metaphylene dimethylamine
CN1974559A (en) * 2006-12-21 2007-06-06 天津大学 Skeleton nickel catalyzed 5-nitrobenzimidazole ketone reducing process for preparing 5-aminobenzimidazole ketone
CN101182295A (en) * 2007-12-14 2008-05-21 浙江工业大学 Method for synthesizing 2-amido-5-chlorobenzotrifluoride

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103497112A (en) * 2013-09-18 2014-01-08 葫芦岛天启晟业化工有限公司 Method for preparing p-chloroaniline without adding organic solvent
CN103497112B (en) * 2013-09-18 2015-07-22 葫芦岛天启晟业化工有限公司 Method for preparing p-chloroaniline without adding organic solvent
CN111302956A (en) * 2020-04-14 2020-06-19 国药集团化学试剂有限公司 Preparation method of 4-bromo-2-aminophenol

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Application publication date: 20120704