CN105618055A - Application of nickel-based catalyst in selective hydrogenation reaction of aromatic nitro compound - Google Patents
Application of nickel-based catalyst in selective hydrogenation reaction of aromatic nitro compound Download PDFInfo
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- CN105618055A CN105618055A CN201410592032.5A CN201410592032A CN105618055A CN 105618055 A CN105618055 A CN 105618055A CN 201410592032 A CN201410592032 A CN 201410592032A CN 105618055 A CN105618055 A CN 105618055A
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- 0 C=C(C=C(C=C[N+]([O-])=O)S1)C1=* Chemical compound C=C(C=C(C=C[N+]([O-])=O)S1)C1=* 0.000 description 3
- YZFWYRMJORJLKI-ONEGZZNKSA-N [O-][N+](/C=C/C1=CCCO1)=O Chemical compound [O-][N+](/C=C/C1=CCCO1)=O YZFWYRMJORJLKI-ONEGZZNKSA-N 0.000 description 1
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Abstract
An application of a nickel-based catalyst in selective hydrogenation reaction of an aromatic nitro compound is disclosed. An active component of the catalyst is nickel, and a carrier is a carbon material. Content of the active component is 0.01-50%. The catalyst shows very high activity and selectivity on the aspect of aromatic nitro compound selective hydrogenation. In comparison with an existing industrial synthetic route of aromatic nitro compound selective hydrogenation, the invention has the following remarkable advantages: reaction process is green and environmentally friendly, operation is simple, and cost is saved.
Description
Technical field
The present invention relates to the application in aromatic nitro compound selective hydrogenation reaction of a kind of nickel-base catalyst.
Background technology
Aromatic nitro compound selective hydrogenation obtains corresponding functionalization aniline or oxime has important application in many aspects, such as in pesticide, medicine, dyestuff and high molecular polymer etc. Hydrogenation for simple aromatic nitro compound, industrially there is the technology of maturation, but during for group that substituent group is reducibility, when existing such as carbon-carbon double bond, triple carbon-carbon bonds C=O bond, carbon nitrogen three key etc., optionally by nitroreduction, and retain double bond and be not hydrogenated, an or challenging problem. Industrially, for the selective hydrogenation of the aromatic nitro compound containing reducibility group, it is generally adopted the reducing agent of metering, as adopted Na2S2O4, ammonia adds Fe, Zn, Sn etc. as reducing agent, but such reducing agent, while obtaining the target product of a mole, produce the garbage of a mole to I haven't seen you for ages, in order to overcome this shortcoming, researcheres are with hydrogen for reducing agent, by PbO or H3PO2Add on loaded Pt catalyst, although reduce activity, but the selectivity for target product improves, but such catalyst can produce phenylhydroxylamine intermediate product, though this by-product under very low level it can also happen that blast danger. Researcher discovery is separately added into iron salt in this catalyst system and catalyzing or this intermediate product can be converted into target product by vitriol salt, but remains substantial amounts of transition metal salt, follow-up complex disposal process in solution after reaction, is not very economical and environmental protection. Therefore one is found for this kind of anti-emergency requirement and there is high activity, high selective heterogeneous catalyst.
Many patents and document describe selective hydrogenation load type gold and the platinum catalyst of aromatic nitro compound, and different with carrier and preparation method, its activity is also not quite similar.
Document 1 (WO2007116111-A1) finds Au/TiO2And Au/Fe2O3Catalyst shows good selectivity in the selective hydrogenation of aromatic nitro compound, and the nitro that the high selective reason of author investigation discovery is aromatic nitro compound can be preferentially adsorbed on Au and TiO2The interface of carrier, so that nitro is preferentially reduced, shows high selectivity.
Document 2 (J.Phys.Chem.C2009,113,17803 17810) is prepared for Au/Al by the method for sol deposition2O3Catalyst, equally to showing good selectivity and specific activity Au/TiO in such selective hydrogenation2High. But the shortcoming of Au catalyst is that the dissociation capability to hydrogen is poor, and the condition therefore reacted is all harsher, and reaction temperature is more than 100 DEG C, and pressure is also at more than 1Mp.
Document 3 (Adv.Synth.Catal.2011,353,1,260 1264) adopts one kettle way to be prepared for a kind of porous ion copolymer and supports Pt catalyst, and the loading of Pt is 4.9wt%, and the Pt Nanoparticle Size obtained is 2-4nm. It is at room temperature R=F, Cl, Br, I, CHO, CN, NH to substituent group2��CH3CO, OH etc. show high activity and selectivity, but are-C=C-for substituent group, and the selectivity shown is very low.
Document 4 (JournalofCatalysis265 (2009) 19 25) utilizes Au catalyst to have high selectivity for aromatic nitro compound, and Pt is the metal that a kind of hydrogenation activity is good, the two respective characteristic is combined, in such reaction, phenotype has gone out good cooperative effect, and author is at Au/TiO2Catalyst mixes 0.01%Pt, at 85 DEG C, 8barPH2The selectivity of 94.5% conversion ratio and 93.4% can be obtained under reaction condition.
Document 5 (WO2009071727) adopts infusion process to be prepared for Pt/TiO2Catalyst, at 40 DEG C, 3barPH2Reaction condition under, in the selective hydrogenation for 3-nitrostyrolene, when loading is 0.2%, it is necessary to reaction 7h could be able to obtain 92% productivity, selectivity is 93.1%.
Summary of the invention
It is an object of the invention to adopt cheap base metal Raney nickel to replace noble metal catalyst, this catalyst shows high activity and selectivity on the hydrogenation of aromatic nitro compound, reaction condition is gentle, catalyst reusable edible, good stability, cheap, there is the prospect of commercial Application. For achieving the above object, technical scheme provided by the invention is:
The application in aromatic nitro compound selective hydrogenation reaction of a kind of nickel-base catalyst, the active component of described nickel-base catalyst is nickel, and carrier is Carbon Materials, and in nickel-base catalyst, the mass content of active component is 0.01%-50%.
Active component is Ni, and in nickel-base catalyst, active component mass content is 0.01-20wt%.
The preparation process of nickel-base catalyst is as follows,
1) in required ratio, the solubility precursor solution of nickel is mixed homogeneously with Carbon Materials, under room temperature after dry 4-24 hour, continue dry 1-10 hour in 50-200 DEG C;
In solution, the solubility precursor concentration of nickel is 0.1-100mg/ml;
The soluble precursor of described active component nickel is one or two or more kinds in nickel nitrate, Nickel dichloride., nickel acetate, nickel sulfate;
2) catalyst needs through reduction treatment before being used for reaction, and reducing atmosphere is the gaseous mixture of hydrogen or the hydrogen volume concentration hydrogen be more than or equal to 10% and noble gas, and reduction temperature is 50 DEG C-800 DEG C, recovery time 10-300min.
Described Carbon supports material is one or two or more kinds in activated carbon, acetylene black, mesoporous carbon material (CMK-3 etc.);
Reacting in airtight autoclave and carry out, in reactor, initial pressure during hydrogen room temperature is 0.1-5Mpa, and reaction temperature is 20-150 DEG C, and the response time was no less than 10 minutes.
Described reacting in solvent carries out, and the solvent adopted is one or two or more kinds in ethanol, methanol, toluene, oxolane, dodecane, water, reaction substrate aromatic nitro compound concentration 0.001-10mol/L in reaction solution;
Reaction substrate is aromatic nitro compoundAnd/orSubstituent R is the one in hydrogen, halogen, vinyl, acetenyl, itrile group, aldehyde radical, phenolic hydroxyl group, carbonyl, methyl, isopropyl, methoxyl group, and the number of substituent R is 1-5; Or reaction substrate is OrIn one, substituent R is the one in hydrogen, halogen, vinyl, acetenyl, itrile group, aldehyde radical, phenolic hydroxyl group, carbonyl, methyl, isopropyl, methoxyl group, and the number of substituent R is 1-5.
The mol ratio of catalyst activity component and reaction substrate is 1 �� 10-4Between 1.
Preferred reaction temperature is 20-80 DEG C, the preferred initial pressure 0.1-1.5Mpa of hydrogen in reactor under room temperature, it is preferable that response time 0.5h-3h.
Catalyst can recycle more than 2 times, and its conversion ratio and selectivity are not decreased obviously, and catalyst easily separates with reaction solution.
The activity test method of catalyst provided by the invention is as follows:
Reactor is autoclave, reaction substrate becomes certain density reactant liquor with interior standard configuration, and every secondary response pipet takes a certain amount of reactant liquor and reacts, and in reactor, initial pressure during hydrogen room temperature is 0.1-5Mpa, reaction temperature is 20-150 DEG C, and the response time was no less than 10 minutes. After reaction end is cooled to room temperature, sampling carries out gas chromatographic analysis.
The present invention has the effect that
1. aromatic nitro compound selective hydrogenation obtains corresponding function aniline or oxime has application at numerous areas, such as agricultural, medicine, dyestuff and high molecular polymer etc. The present invention provides a kind of nickel-base catalyst highly selective catalysis can obtain functionalization aniline or oxime.
2. the present invention provides a kind of nickel-base catalyst in the reaction of aromatic nitro compound selective hydrogenation, can recycle repeatedly, and activity does not substantially reduce.
3. catalyst provided by the invention is after the reaction, it is easy to separate from reaction solution, easy and simple to handle.
In a word, present invention achieves aromatic nitro compound selective conversion efficient, high and prepare functionalization aniline or oxime, compared with existing industrial catalyst system, catalyst provided by the invention is green friendly in the process of this kind of reaction, save cost, be expected to industrially be applied.
Accompanying drawing explanation
The TEM figure of Fig. 1 difference loading Ni/AC catalyst. As can be seen from the figure the particle size of the catalyst nickel of different loadings is 5-7nm, and is evenly distributed.
Detailed description of the invention
Embodiment 1:0.05g nickel nitrate is dissolved in 1.3g deionized water, nickel nitrate solution upon dissolution adds 1g absorbent charcoal carrier, after being uniformly mixed after dry at room temperature over night, puts into 80 DEG C of oven drying 5h, obtain 1%Ni/AC, stand-by in exsiccator;
Embodiment 2:0.25g nickel nitrate is dissolved in 1.3g deionized water, nickel nitrate solution upon dissolution adds 1g absorbent charcoal carrier, after being uniformly mixed after dry at room temperature over night, puts into 80 DEG C of oven drying 5h, obtain 5%Ni/AC, stand-by in exsiccator;
Embodiment 3:0.5g nickel nitrate is dissolved in 1.3g deionized water, nickel nitrate solution upon dissolution adds 1g absorbent charcoal carrier, after being uniformly mixed after dry at room temperature over night, puts into 80 DEG C of oven drying 5h, obtain 10%Ni/AC, stand-by in exsiccator;
Embodiment 4:1g nickel nitrate is dissolved in 1.3g deionized water, adds 1g absorbent charcoal carrier, after being uniformly mixed after dry at room temperature over night, put into 80 DEG C of oven drying 5h, obtain 20%Ni/AC in nickel nitrate solution upon dissolution, stand-by in exsiccator;
Embodiment 5:0.25g nickel nitrate is dissolved in 1.0g deionized water, adds 1gAl in nickel nitrate solution upon dissolution2O3Carrier, after being uniformly mixed after dry at room temperature over night, puts into 80 DEG C of oven drying 5h, obtains 5%Ni/Al2O3, stand-by in exsiccator;
Embodiment 6:0.25g nickel nitrate is dissolved in 0.6g deionized water, adds 1gSiO in nickel nitrate solution upon dissolution2Carrier, after being uniformly mixed after dry at room temperature over night, puts into 80 DEG C of oven drying 5h, obtains 5%Ni/SiO2, stand-by in exsiccator;
Application examples 1
Catalyst both passes through volume content 10%H before use2/ He reduces, reducing condition is that 10 DEG C/min is raised to 350 DEG C, after reduction 30min, 30min is purged with He, take out rapidly and weigh 0.1g and pour in reaction tube, add the 3-nitrostyrolene reactant liquor (toluene is solvent, and o-Dimethylbenzene is interior mark) of 5ml0.1M with pipet, reaction condition is 3barH2(initial pressure), 40 DEG C.
Specific experiment result is as follows:
The different nickel loading catalyst of table one selects the result of hydrogenation at 3-nitrostyrolene
As seen from table along with the increase of loading, the selectivity of target product is not substantially reduced, it is advantageous to loading 5%.
Table two different carriers selects the result of hydrogenation at 3-nitrostyrolene
By data in table it can be seen that activated carbon is carrier compares Al2O3And SiO2Show higher selectivity.
Table three 5%Ni/AC catalyst selects the circulation experiment result of hydrogenation at 3-nitrostyrolene
By data in table it can be seen that catalyst is after circulation four times, activity and selectivity is not decreased obviously, it was shown that the good cycling stability of catalyst.
Table four 5%Ni/AC selects the result of hydrogenation at differential responses substrate
Be can be seen that this catalyst has significantly high selectivity equally for other substrates by data in table.
Application examples 2:
Catalyst both passes through 10%H before use2/ He reduces, and reducing condition is that 10 DEG C/min is raised to 350 DEG C, after reduction 30min, purges 30min with He, takes out rapidly and weigh 0.1g and pour in reaction tube, adds the reactant of 0.5mmol, and reaction condition is 2MpH2, 60 DEG C, ethanol is solvent.
Table five 5%Ni/AC catalyst catalysis activity on different substrates is investigated.
Result of study shows that Ni/AC catalyst selects Hydrogenation for showing good universality on oxime at the unsaturated nitro compound of ��, ��.
The TEM figure of Fig. 1 difference loading Ni/AC catalyst, as can be seen from the figure the particle size of the catalyst nickel of different loadings is 5-7nm, and is evenly distributed.
Claims (9)
1. the nickel-base catalyst application in aromatic nitro compound selective hydrogenation reaction, it is characterised in that: the active component of described nickel-base catalyst is nickel, and carrier is Carbon Materials, and in nickel-base catalyst, the mass content of active component is 0.01%-50%.
2. apply as claimed in claim 1, it is characterised in that: active component is Ni, and in nickel-base catalyst, active component mass content is 0.01-20wt%.
3. apply as claimed in claim 1, it is characterised in that: the preparation process of nickel-base catalyst is as follows,
1) in required ratio, the solubility precursor solution of nickel is mixed homogeneously with Carbon Materials, under room temperature after dry 4-24 hour, continue dry 1-10 hour in 50-200 DEG C;
In solution, the solubility precursor concentration of nickel is 0.1-100mg/ml;
The soluble precursor of described active component nickel is one or two or more kinds in nickel nitrate, Nickel dichloride., nickel acetate, nickel sulfate;
2) catalyst needs through reduction treatment before being used for reaction, and reducing atmosphere is the gaseous mixture of hydrogen or the hydrogen volume concentration hydrogen be more than or equal to 10% and noble gas, and reduction temperature is 50 DEG C-800 DEG C, recovery time 10-300min.
4. the application as described in claim 1 or 3, it is characterised in that: described Carbon supports material is one or two or more kinds in activated carbon, acetylene black, mesoporous carbon material (CMK-3 etc.).
5. apply as claimed in claim 1, it is characterised in that:
Reacting in airtight autoclave and carry out, in reactor, initial pressure during hydrogen room temperature is 0.1-5Mpa, and reaction temperature is 20-150 DEG C, and the response time was no less than 10 minutes.
6. the application as described in claim 1 or 5, it is characterised in that:
Described reacting in solvent carries out, and the solvent adopted is one or two or more kinds in ethanol, methanol, toluene, oxolane, dodecane, water, reaction substrate aromatic nitro compound concentration 0.001-10mol/L in reaction solution;
Reaction substrate is aromatic nitro compoundAnd/orSubstituent R is the one in hydrogen, halogen, vinyl, acetenyl, itrile group, aldehyde radical, phenolic hydroxyl group, carbonyl, methyl, isopropyl, methoxyl group, and the number of substituent R is 1-5; Or reaction substrate is OrIn one, substituent R is the one in hydrogen, halogen, vinyl, acetenyl, itrile group, aldehyde radical, phenolic hydroxyl group, carbonyl, methyl, isopropyl, methoxyl group, and the number of substituent R is 1-5.
7. the application as described in claim 1 or 5, it is characterised in that:
The mol ratio of catalyst activity component and reaction substrate is 1 �� 10-4Between 1.
8. the application as described in claim 1 or 5, it is characterised in that:
Preferred reaction temperature is 20-80 DEG C, the preferred initial pressure 0.1-1.5Mp of hydrogen in reactor under room temperature, it is preferable that response time 0.5-3h.
9. apply as claimed in claim 1, it is characterised in that: catalyst can recycle more than 2 times, and its conversion ratio and selectivity are not decreased obviously, and catalyst easily separates with reaction solution.
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| CN107199039A (en) * | 2017-06-29 | 2017-09-26 | 浙江工业大学 | A kind of metallic nickel insertion porous charcoal coating ceramic honey comb integral catalyzer and application |
| CN107308937A (en) * | 2017-06-30 | 2017-11-03 | 青岛科技大学 | A kind of hydrothermal preparing process of carbon base catalyst for paranitrophenol catalytic hydrogenation |
| CN107570157A (en) * | 2017-09-15 | 2018-01-12 | 青岛科技大学 | A kind of preparation method for the order mesoporous Pd/carbon catalyst for preparing p-aminophenol |
| CN110354857A (en) * | 2019-08-19 | 2019-10-22 | 天津理工大学 | A kind of preparation method and applications of Ni-based heterogeneous catalyst are in catalysis aldehyde compound hydrogenation deoxidation reaction |
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| CN102285891A (en) * | 2011-06-30 | 2011-12-21 | 浙江工业大学 | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound |
| CN103772207A (en) * | 2014-03-05 | 2014-05-07 | 湖北大学 | Method for preparing cyclohexylamine with high selectivity from nitrobenzene in one-step catalytic hydrogenation mode |
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Patent Citations (5)
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| US6140539A (en) * | 1999-03-03 | 2000-10-31 | Basf Aktiengesellschaft | Preparation of amines |
| CN101020136A (en) * | 2007-03-03 | 2007-08-22 | 大连理工大学 | Prepn of nanometer carbon material supported metal catalyst for hydrogenating chloronitrobenzene to synthesize chloroaniline |
| CN101693201A (en) * | 2009-10-16 | 2010-04-14 | 南京工业大学 | Mesopore carbon load nickel hydrogenation catalyst and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107199039A (en) * | 2017-06-29 | 2017-09-26 | 浙江工业大学 | A kind of metallic nickel insertion porous charcoal coating ceramic honey comb integral catalyzer and application |
| CN107199039B (en) * | 2017-06-29 | 2020-04-21 | 浙江工业大学 | Metallic nickel embedded porous carbon coated honeycomb ceramic monolithic catalyst and application thereof |
| CN107308937A (en) * | 2017-06-30 | 2017-11-03 | 青岛科技大学 | A kind of hydrothermal preparing process of carbon base catalyst for paranitrophenol catalytic hydrogenation |
| CN107308937B (en) * | 2017-06-30 | 2020-10-23 | 青岛科技大学 | Application of carbon-based catalyst in catalytic hydrogenation reaction of p-nitrophenol |
| CN107570157A (en) * | 2017-09-15 | 2018-01-12 | 青岛科技大学 | A kind of preparation method for the order mesoporous Pd/carbon catalyst for preparing p-aminophenol |
| CN110354857A (en) * | 2019-08-19 | 2019-10-22 | 天津理工大学 | A kind of preparation method and applications of Ni-based heterogeneous catalyst are in catalysis aldehyde compound hydrogenation deoxidation reaction |
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Application publication date: 20160601 |