CN107540553B - Method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene - Google Patents
Method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene Download PDFInfo
- Publication number
- CN107540553B CN107540553B CN201610486455.8A CN201610486455A CN107540553B CN 107540553 B CN107540553 B CN 107540553B CN 201610486455 A CN201610486455 A CN 201610486455A CN 107540553 B CN107540553 B CN 107540553B
- Authority
- CN
- China
- Prior art keywords
- nitronaphthalene
- naphthylamine
- supported
- nickel
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene. Using supported Ni2P is a catalyst and is at 413-453K, 3.0-5.0 MPa and mass airspeed of 0.25-0.5 h‑1The trickle bed catalytic hydrogenation reaction is carried out, the complete conversion of the 1-nitronaphthalene can be realized, and the selectivity of the 1-naphthylamine is 100 percent.
Description
Technical Field
The invention relates to a method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene, belonging to the technical field of catalytic hydrogenation.
Technical Field
1-naphthylamine, also known as α -naphthylamine and methylnaphthylamine, is an important dye intermediate, is also a main raw material of rubber antioxidant AP, antioxidant AH and the like, and can be used for producing pesticides, 1-naphthol and other products.
The traditional process for industrially producing 1-naphthylamine uses refined naphthalene as raw material, prepares 1-nitronaphthalene by mixed acid nitration, and then prepares 1-naphthylamine by sodium sulfide or iron powder reduction method, although the technology is simple and mature, the product quality is poor, the labor intensity is large, the production cost is high, and a large amount of industrial waste which is difficult to treat is produced as a byproduct, thereby causing serious environmental pollution and human health. Therefore, there have been some patented technologies for producing 1-naphthylamine by using a catalytic hydrogenation process instead of the conventional process. The catalytic hydrogenation process has high product yield and good quality, basically has no three wastes, and is environment-friendly.
The existing catalytic hydrogenation process for synthesizing naphthylamine mainly adopts Pt/C, Pd/C and other noble metal catalysts and Raney nickel catalysts. The noble metal catalyst is expensive and is less adopted in China. Raney nickel catalysts are typically used for batch reactions. The supported nickel catalyst is low in cost and easy to obtain, has high activity and is also researched more. CN102304053 discloses a method for preparing naphthylamine by catalyzing hydrogenation of nitronaphthalene ethanol solution with a nickel-copper composite catalyst, wherein the reaction pressure is 3-5 MPa, the temperature is 80-120 ℃, the reaction time is 4-15 hours, and the reaction conversion rate and the naphthylamine yield are not lower than 99%. However, the nickel-copper composite catalyst used in the process is prepared from alkali-soluble nickel-copper-aluminum alloy, has the similar defect as a Raney nickel catalyst, and can only be used for carrying out intermittent hydrogenation reaction in a kettle type reactor. CN101434550 discloses a method for preparing 1-naphthylamine by carrying out catalytic hydrogenation on 1-nitronaphthalene in a reaction kettle by using a supported nickel catalyst and ethanol as a solvent, wherein hydrogenation is carried out for 3-8 hours at 60-90 ℃ and 1.5-3.0 MPa, and the conversion rate reaches 95-99%. At present, related research in China stays in a small-scale test scale, and no industrial report is found. Although the catalytic hydrogenation method for synthesizing naphthylamine belongs to an advanced clean production process, the raw material nitronaphthalene contains about 2% of benzothiophene, so that the hydrogenation catalyst is easily poisoned, and the method is a difficult problem to be solved urgently in industrial production (CN 101973894). Therefore, the research and development of the low-cost, high-activity, high-selectivity and sulfur-toxicity-resistant hydrogenation catalyst has important practical value for promoting the catalytic hydrogenation of 1-nitronaphthalene to synthesize 1-naphthylamine.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a method for using supported Ni in a trickle bed2The P catalyst is used for carrying out catalytic hydrogenation on 1-nitronaphthalene to synthesize 1-naphthylamine. The trickle bed reaction condition is mild, the product yield is high, the problem of separation of the catalyst and the product is avoided, the reaction is more efficient than batch kettle type reaction, and the method is suitable for industrial continuous production.
Catalysts suitable for use in trickle bed reactors must be shaped catalysts and, at the same time, require relatively stable properties to maintain an active life over extended periods of time when using sulfur-containing feedstocks. The invention uses supported Ni2The P catalyst has strong sulfur poisoning resistance due to the special crystal lattice, and can meet the production process requirement of preparing 1-naphthylamine by continuous catalytic hydrogenation by using a sulfur-containing 1-nitronaphthalene raw material in a trickle bed.
The invention has another innovation point that piperidine is added into the raw materials. On one hand, piperidine is used as a solvent, has better solubility to 1-nitronaphthalene and products, has low boiling point and latent heat, and is easy to separate; on the other hand, piperidine is added into the raw materials to inhibit the cracking of reactants and products and the condensation between 1-naphthylamine molecules obtained by reduction, thereby improving the selectivity and stability of the catalytic hydrogenation reaction of 1-nitronaphthalene.
By adopting the method provided by the invention, under the optimized condition, the hydrogenation conversion rate of the 1-nitronaphthalene can reach 100%, and the selectivity of the 1-naphthylamine is 100%.
The technical scheme of the invention is as follows:
in trickle bed reactors, using supported Ni2The P catalyst uses a mixture of 1-nitronaphthalene and piperidine as a raw material, and the 1-nitronaphthalene is catalytically hydrogenated into 1-naphthylamine in a hydrogen atmosphere.
The above-mentioned supported Ni2The P catalyst is prepared by phosphating a supported nickel catalyst precursor.
The nickel content in the supported nickel catalyst precursor is 40-80% by mass of nickel element, and the supported nickel catalyst precursor exists in the form of metallic nickel or nickel oxide. The supported nickel catalyst precursor is prepared by a precipitation method.
The phosphating of the supported nickel catalyst precursor may be carried out by a gas or liquid phase phosphating process, preferably a liquid phase phosphating process, such as the phosphating process disclosed in CN 104772154.
The reaction conditions for the catalytic hydrogenation of 1-nitronaphthalene to 1-naphthylamine are as follows: the mass percentage of the 1-nitronaphthalene in the raw material of the mixture of the 1-nitronaphthalene and the piperidine is 5-15%, and the mass percentage of the piperidine is 85-95%; the reaction temperature is 393-493K, preferably 413-453K; the reaction pressure is 2.0-6.0 MPa, preferably 3.0-5.0 MPa; space velocity (supported Ni by 1-nitronaphthalene pair)2P catalyst mass) for 0.2-1 h-1Preferably 0.25 to 0.5 hour-1(ii) a The ratio of the amount of the hydrogen to the amount of the 1-nitronaphthalene substance is 3-15: 1, preferably 6-12: 1.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
100ml of Ni (NO) containing 14.9g3)2·6H2O、11.1g Mg(NO3)2·6H2O and 1.8g Al (NO)3)3·9H2Aqueous solution of O and equal volume of Na containing 11.9g2CO3Is simultaneously added dropwise to 100ml of vigorously stirred distilled waterIn the process, a green precipitate is formed, the filter cake is washed clean and then dispersed into 200ml of n-butanol, the solvent is distilled off at 353K, and the drying is continued at 393K. Tabletting and crushing the obtained powder, and screening 20-40 mesh granules.
Taking 5g of the particles, diluting to 15ml with quartz sand, filling into a fixed bed reaction tube, reducing at 723K for 2h in flowing hydrogen at 200ml/min, cooling to room temperature, and adding a catalyst containing 0.5% (v/v) O2N of (A)2Passivating for 24 hours to obtain the supported nickel catalyst precursor, wherein the mass percentage of the nickel element is about 60 percent.
Example 2
1g of the supported nickel catalyst precursor prepared in the example 1 is diluted to 3ml by quartz sand, filled into a fixed bed reaction tube, reduced for 2h at 523K in flowing hydrogen at 40ml/min, then cooled to 443K, introduced with n-heptane solution containing 2% triphenylphosphine for phosphorization for 24h, then heated to 523K, and continuously introduced with hydrogen for 3h to obtain supported Ni2And (3) a P catalyst. Will support Ni2And (3) reducing the temperature of the P catalyst to 433K, increasing the hydrogen pressure to 3.0MPa, and pumping the 1-nitronaphthalene/piperidine mixture with the mass ratio of 1/9 into a reactor by using a metering pump to perform catalytic hydrogenation reaction. 1-nitronaphthalene pair supported Ni2The mass space velocity of the P catalyst is 0.5h-1The ratio of the amount of hydrogen to 1-nitronaphthalene species was 10: 1. The product was analyzed, the conversion of 1-nitronaphthalene was 100%, and the selectivity of 1-naphthylamine was 100%.
Claims (4)
1. A method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene is characterized in that: in a trickle bed reactor, using a supported Ni2P catalyst, using a mixture of 1-nitronaphthalene and piperidine as a raw material, and catalytically hydrogenating the 1-nitronaphthalene into 1-naphthylamine in a hydrogen atmosphere; the mass percentage of the 1-nitronaphthalene in the raw material of the mixture of the 1-nitronaphthalene and the piperidine is 5-15%, and the mass percentage of the piperidine is 85-95%.
2. The supported Ni2P catalyst of claim 1, produced by phosphating a supported nickel catalyst precursor.
3. The supported nickel catalyst precursor according to claim 2, wherein the nickel content is 40 to 80% by mass of the nickel element, and the nickel element is present in the form of metallic nickel or nickel oxide.
4. The process of claim 1, wherein the reaction conditions for the catalytic hydrogenation of 1-nitronaphthalene to 1-naphthylamine are as follows: (ii) a The reaction temperature is 393-493K; the reaction pressure is 2.0-6.0 MPa; the mass space velocity of the supported Ni2P catalyst is 0.2-1 h < -1 >; the ratio of the amount of the hydrogen to the amount of the 1-nitronaphthalene substance is 3-15: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610486455.8A CN107540553B (en) | 2016-06-23 | 2016-06-23 | Method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610486455.8A CN107540553B (en) | 2016-06-23 | 2016-06-23 | Method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107540553A CN107540553A (en) | 2018-01-05 |
| CN107540553B true CN107540553B (en) | 2020-04-24 |
Family
ID=60962331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610486455.8A Active CN107540553B (en) | 2016-06-23 | 2016-06-23 | Method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107540553B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407707A (en) * | 2018-04-26 | 2019-11-05 | 南京大学 | A kind of method that catalytic hydrogenation prepares aniline |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434550A (en) * | 2008-11-07 | 2009-05-20 | 甘肃中科药源生物工程有限公司 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
| CN102304053A (en) * | 2011-07-22 | 2012-01-04 | 湖南化工研究院 | Preparation method for synthesizing naphthylamine by catalytic hydrogenation |
| CN103566956A (en) * | 2013-11-22 | 2014-02-12 | 安徽师范大学 | Micron-size nickel phosphide material as well as preparation method and application of micron-size nickel phosphide material |
| CN104383948A (en) * | 2014-10-31 | 2015-03-04 | 常州大学 | Preparation method of siliceous mesocellular foams (MCFs) loaded nano Ni2P hydrogenation catalyst |
| CN104941673A (en) * | 2015-05-13 | 2015-09-30 | 大连理工大学 | Nickel phosphide catalyst containing sulphur and application of nickel phosphide catalyst |
-
2016
- 2016-06-23 CN CN201610486455.8A patent/CN107540553B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434550A (en) * | 2008-11-07 | 2009-05-20 | 甘肃中科药源生物工程有限公司 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
| CN102304053A (en) * | 2011-07-22 | 2012-01-04 | 湖南化工研究院 | Preparation method for synthesizing naphthylamine by catalytic hydrogenation |
| CN103566956A (en) * | 2013-11-22 | 2014-02-12 | 安徽师范大学 | Micron-size nickel phosphide material as well as preparation method and application of micron-size nickel phosphide material |
| CN104383948A (en) * | 2014-10-31 | 2015-03-04 | 常州大学 | Preparation method of siliceous mesocellular foams (MCFs) loaded nano Ni2P hydrogenation catalyst |
| CN104941673A (en) * | 2015-05-13 | 2015-09-30 | 大连理工大学 | Nickel phosphide catalyst containing sulphur and application of nickel phosphide catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 负载型磷化镍催化剂的制备及其应用的研究进展;井晓慧 等;《石油化工》;20151115;第44卷(第11期);第1409-1416页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107540553A (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102807483B (en) | Method for preparing cyclopentanone and/or cyclopentanol by furfural or furfuryl alcohol | |
| CN101844976B (en) | Method for preparing butanedioic acid under catalytic hydrogenation | |
| CN107500296B (en) | A kind of rodlike β-Mo2The controlledly synthesis of C and its application in inverse water gas shift reation | |
| CN110961110B (en) | Catalyst and application thereof in 2,3,6-trichloropyridine hydrodechlorination | |
| CN103848719B (en) | Method for preparing 1,5-pentanediol via selective hydrogenolysis of tetrahydrofurfuryl alcohol | |
| CN110467517A (en) | A kind of hydrogenation of acetophenone prepares the method and catalyst of alpha-phenyl ethyl alcohol | |
| CN105879874A (en) | High-dispersion loaded nickel catalyst and preparation method thereof | |
| CN107540553B (en) | Method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene | |
| CN102744085A (en) | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation | |
| CN110756198A (en) | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof | |
| CN106890665A (en) | A kind of catalyst of Dimethyl ether carbonylation production methyl acetate and its application | |
| CN105618063B (en) | It is a kind of for beta-diketon Hydrogenation for beta-diol catalyst | |
| CN110368946A (en) | The method that carried non-crystal alloy catalysis hydrogenation of acetophenone prepares alpha-phenyl ethyl alcohol | |
| CN103450026B (en) | Synthesis method of N, N-diethylpropargylamine as electroplating additive | |
| CN103709018B (en) | Method for preparing guaiacol | |
| CN112138676B (en) | Catalyst for preparing o-phenylphenol and preparation method thereof | |
| CN107056573B (en) | Method for producing trans-decalin by naphthalene hydrogenation | |
| CN101531574B (en) | Method for preparing 3,4,5-trimethoxy toluene | |
| CN114522716A (en) | Bimetal supported catalyst, preparation method thereof and application of bimetal supported catalyst in preparation of biological aviation kerosene through palm oil hydro-conversion | |
| CN104525193B (en) | A kind of preparation method of producing cyclohexene with benzene selective hydrogenation loaded catalyst | |
| CN112717941A (en) | Ester hydrogenation catalyst, and preparation method and application thereof | |
| CN115382556B (en) | Cu-Ru bimetal doped titanium-silicon metal composite oxide catalyst and application thereof in catalytic hydrogenation of triacetonamine | |
| CN110407707A (en) | A kind of method that catalytic hydrogenation prepares aniline | |
| CN109926051A (en) | A kind of preparation method of the Raney nickel for 1- nitronaphthalene catalytic hydrogenation | |
| CN114192142B (en) | Catalyst for dinonyl phenol hydrogenation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |