CN101161631A - Preparation method of cyclohexylamine - Google Patents
Preparation method of cyclohexylamine Download PDFInfo
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- CN101161631A CN101161631A CNA2006101136201A CN200610113620A CN101161631A CN 101161631 A CN101161631 A CN 101161631A CN A2006101136201 A CNA2006101136201 A CN A2006101136201A CN 200610113620 A CN200610113620 A CN 200610113620A CN 101161631 A CN101161631 A CN 101161631A
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- phenol
- hexahydroaniline
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Abstract
The present invention discloses a preparation method of cyclohexylamine, in which phenol, H2, and NH3 are adopted as the raw materials, the catalyst used by the present invention adopts gamma-Al2O3 as the carrier skeleton, and magnesia-alumina spinal carrier is made through impregnating the mixed solution of nitric magnesium and nitric aluminum, then the chloride palladium hydrochloric acid solution is impregnated to obtain the hydrogenated and aminated catalyst of Pd/Al2O3-MgO/Al2O3. Then the catalyst is added into an integral reactor, firstly activated under ordinary pressure through conducting the hydrogen gas, then phenyl, hydrogen gas and ammonia gas in proportion under about 180 DEG C are conducted to produce cyclohexylamine. Compared with the aniline hydrogenation reduction generally adopted both domestically and worldwide, the present invention with simple technics has the advantages of firstly low cost, with cheaper phenol to substitute for aniline as the raw material for the preparation of cyclohexylamine; secondly the catalyst with high activity and a long life ; thirdly high yield of product with high selectivity and 4, minor pollution, with capability to meet the principle of green chemical industrial technology.
Description
Technical field:
The invention belongs to the preparation technology of Chemicals hexahydroaniline.
Background technology:
Hexahydroaniline (has another name called hexahydrophthalic anilide or amino bad hexane, English name cyclohexylamine) is important fine-chemical intermediate, is mainly used in and produces petroleum products additive, metal inhibitor, thiofide and products such as anti-aging agent, food and feed additive.Mainly contain four kinds of operational paths at present, i.e. aniline hydrogenating reduction method, nitrocyclohexane reduction method, pimelinketone catalytic ammoniation method and hexalin catalytic ammoniation method.It is domestic that what generally adopt is aniline hydrogenating reduction method.This Technology maturation, raw material is easy to get, and yield is also very high, but the traditional processing technology of raw materials used aniline can produce bigger pollution to environment, and cost is higher.Along with the rise of green chemical industry technology, all developed the novel process that aniline is produced in the phenol ammonification both at home and abroad energetically in the last few years.The present invention produces hexahydroaniline with the direct hydrogenation amination of phenol, not only can reduce production costs, and also meets the principle of green chemical industry technology.
Summary of the invention:
The method that the purpose of this invention is to provide a kind of environmental protection, low cost, easy synthesizing cyclohexane 1 amine.The preparation technology of this hexahydroaniline comprises two contents: (one) palladium load magnesium-aluminium spinel Preparation of catalysts; (2) by phenol hydrogenation ammonification synthesizing cyclohexane 1 amine.
Earlier with quantitative γ-Al
2O
3, 250 ℃ of dehydrations down, as carrier framework.Take by weighing Mg (NO again
3)
26H
2O and Al (NO
3)
39H
2O is mixed with mixing solutions, pours this solution into dress γ-Al
2O
3Beaker in, carry out incipient impregnation at twice.Descended dry 6 hours at 120 ℃ then,, obtain the magnesium-aluminium spinel carrier after the cooling 800～1200 ℃ of following roastings 6 hours; Get a certain amount of NaHCO
3Wiring solution-forming, following dry 6 hours behind the impregnated carrier at 120 ℃; Take by weighing quantitative PdCl at last
2, press PdCl
2: the ratio of dilute hydrochloric acid=1: 10 (weight) is with dissolving, and incipient impregnation, drying are carried out at twice with the above-mentioned carrier that makes in the dissolving back, obtain special-purpose Pd (0.5% weight)/(Al
2O
3-MgO)/Al
2O
3The hydrogenation amination catalysis.
With the catalyzer that makes pack into internal diameter be φ 20mm, highly in the stainless steel integral reactor of 600mm, the top and the bottom of catalyzer filling porcelain ring.Earlier about 300 ℃, catalyzer is activated 10 hours with hydrogen, under normal pressure, feed phenol, hydrogen and ammonia then, wherein the mol ratio of phenol and hydrogen, ammonia be 1: 10: 10 o'clock better, the load of catalyzer is (0.6～0.9) moles of phenol/(a Kg catalyzer hour), 170～190 ℃ of temperature of reaction, the transformation efficiency of phenol reaches as high as 94.6%, and the selectivity of hexahydroaniline is 89.4%, the selectivity of dicyclohexyl amine is 7.4%, and all the other are reaction by products such as pimelinketone, aniline.
Simple and the environmental protection of preparation technology of the present invention, the relatively cheap phenol substituted aniline of available rates is as the raw material of preparation hexahydroaniline.The catalyst activity height, the life-span is long, and product selectivity is good, the yield height.
Embodiment:
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1:
The selection mean pore size is that 6～8nm, diameter are γ-Al of φ 3mm
2O
330 grams 250 ℃ of following drying and dehydratings 5 hours, are put into beaker as carrier framework.Take by weighing 8 gram Mg (NO
3)
26H
2O and 6.9 gram Al (NO
3)
39H
2O adds 34 gram distilled water and is mixed with mixing solutions, pours this solution into dress γ-Al
2O
3Beaker in, carry out incipient impregnation at twice.Descended dry 6 hours at 120 ℃ then,, obtain the magnesium-aluminium spinel carrier after the cooling 1000 ℃ of following roastings 6 hours; Take by weighing the NaHCO of 1.5 grams
3Be made into 10ml solution, following dry 6 hours behind the impregnated carrier at 120 ℃; Take by weighing 0.25 gram PdCl again
2, adding 10% dilute hydrochloric acid 10ml and dissolve, incipient impregnation is carried out at twice with the above-mentioned carrier that makes in the dissolving back, is washed with distilled water to no chlorion and sodium ion, then 120 ℃ of dryings 6 hours down, 500 ℃ of following roastings 8 hours.
With the catalyzer that makes pack into internal diameter be φ 20mm, highly in the stainless steel integral reactor of 600mm, the top and the bottom of catalyzer filling porcelain ring.Earlier with hydrogen catalyzer is activated 10 hours at 300 ℃, be cooled to 180 ℃ with nitrogen then, under normal pressure, feed phenol, feed hydrogen and ammonia with the speed of 80ml/min with the speed of 2.0 Grams Per Hours, temperature of reaction remains 180 ℃, the transformation efficiency of phenol is 94.6%, the selectivity of hexahydroaniline is 89.4%, and the selectivity of dicyclohexyl amine is 7.4%.
Embodiment 2:
Catalyst preparation process is with embodiment 1, and the palladium amount of carrying of catalyzer changes 0.2% (weight), MgO: Al into
2O
3=1: 4, MgO+Al
2O
3Total pickup be 10%; The phenol inlet amount is 2.5 Grams Per Hours, and other reaction conditions is constant, and the transformation efficiency of phenol is 94.1%, and the selectivity of hexahydroaniline is 74.5%, and the selectivity of dicyclohexyl amine is 13.6%.
Embodiment 3:
Selecting mean pore size is γ-Al of 12.7nm
2O
3As the support of the catalyst skeleton, catalyst preparation process and preparation condition are with embodiment 1, and reaction conditions is also with embodiment 1, and the transformation efficiency of phenol is 93.1%, and the selectivity of hexahydroaniline is 76.5%, and the selectivity of dicyclohexyl amine is 14.7%.
Embodiment 4:
Directly select γ-Al
2O
3As support of the catalyst, other preparation process of catalyzer is with embodiment 1, and reaction conditions is constant, and the transformation efficiency of phenol is 92.3%, and the selectivity of hexahydroaniline is 51.5%, and the selectivity of dicyclohexyl amine is 43.6%.
Embodiment 5:
Catalyst preparation process is with embodiment 1, and temperature of reaction is 220 ℃, and other reaction conditions is constant, and the transformation efficiency of phenol is 89.1%, and the selectivity of hexahydroaniline is 64.5%, and the selectivity of dicyclohexyl amine is 3.6%, and the selectivity of aniline is 32.6%.
Claims (5)
1. the preparation method of a hexahydroaniline, this method is with phenol, H
2And NH
3Be raw material, it is characterized in that this preparation method's processing condition are: temperature of reaction should maintain 180 ± 10 ℃, and reaction pressure is a normal pressure; The catalyzer that uses is: the palladium series catalyst of making as carrier, of pickling process with magnesium-aluminium spinel.
2. the preparation method of hexahydroaniline according to claim 1 is characterized in that the catalyzer among this preparation method is to adopt γ-Al
2O
3Be carrier framework, by dipping Mg (NO
3)
26H
2O and Al (NO
3)
39H
2The mixing solutions of O is produced the magnesium-aluminium spinel carrier; Flood PdCl again
2Hydrochloric acid soln, make special-purpose Pd/ (Al
2O
3-MgO)/Al
2O
3The hydrogenation amination catalysis.
3. the preparation method of hexahydroaniline according to claim 1 and 2 is characterized in that γ-Al that support of the catalyst is used
2O
3Mean pore size be 6-8nm, wherein the aperture should be greater than 80% less than the ratio that aperture occupied of 10nm.
4. the preparation method of hexahydroaniline according to claim 1 and 2 is characterized in that MgO: Al in the magnesium-aluminium spinel on support of the catalyst surface
2O
3=(1～4): 1.
5. the preparation method of hexahydroaniline according to claim 1 and 2 is characterized in that prepared catalyzer should be with hydrogen activation 10 hours under 300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101136201A CN101161631A (en) | 2006-10-10 | 2006-10-10 | Preparation method of cyclohexylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101136201A CN101161631A (en) | 2006-10-10 | 2006-10-10 | Preparation method of cyclohexylamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101161631A true CN101161631A (en) | 2008-04-16 |
Family
ID=39296622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101136201A Pending CN101161631A (en) | 2006-10-10 | 2006-10-10 | Preparation method of cyclohexylamine |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690204A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing cyclohexanediamine |
| CN109422655A (en) * | 2017-08-24 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of method of the direct ammonification aniline of phenol |
| CN109529826A (en) * | 2018-11-05 | 2019-03-29 | 常州大学 | A kind of continuity method prepares the method and catalyst of cyclohexyl methylamine |
| CN109647450A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Hydrogenation catalyst for synthesizing cyclohexane 1 amine |
| CN109647452A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Prepare the hydrogenation catalyst of cyclohexylamine |
| CN109647454A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Aniline prepares the hydrogenation catalyst of cyclohexylamine |
-
2006
- 2006-10-10 CN CNA2006101136201A patent/CN101161631A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690204A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing cyclohexanediamine |
| CN109422655A (en) * | 2017-08-24 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of method of the direct ammonification aniline of phenol |
| CN109422655B (en) * | 2017-08-24 | 2021-10-29 | 中国石油化工股份有限公司 | Method for preparing aniline by directly ammoniating phenol |
| CN109647450A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Hydrogenation catalyst for synthesizing cyclohexane 1 amine |
| CN109647452A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Prepare the hydrogenation catalyst of cyclohexylamine |
| CN109647454A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Aniline prepares the hydrogenation catalyst of cyclohexylamine |
| CN109647454B (en) * | 2017-10-10 | 2022-02-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst for preparing cyclohexylamine from aniline |
| CN109529826A (en) * | 2018-11-05 | 2019-03-29 | 常州大学 | A kind of continuity method prepares the method and catalyst of cyclohexyl methylamine |
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Open date: 20080416 |