CN101450903B - Method for preparing cyclohexylamine - Google Patents
Method for preparing cyclohexylamine Download PDFInfo
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- CN101450903B CN101450903B CN200710202742A CN200710202742A CN101450903B CN 101450903 B CN101450903 B CN 101450903B CN 200710202742 A CN200710202742 A CN 200710202742A CN 200710202742 A CN200710202742 A CN 200710202742A CN 101450903 B CN101450903 B CN 101450903B
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- preparation
- hexahydroaniline
- magnesium
- phenol
- aluminium spinel
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Abstract
The invention discloses a method for preparing cyclohexylamine. The method comprises: phenol, H2 and NH3 are used as raw materials, at a temperature of between 150 and 260 DEG C, under pressure of between 0.1 and 1MPa, and in the presence of palladium catalyst, the raw materials are reacted to prepare the cyclohexylamine. The method has the advantages of simple process, environmental protection and low cost. The invention belongs to the field of preparing the cyclohexylamine.
Description
Technical field
The present invention relates to a kind of preparation method of hexahydroaniline, relating to a kind of specifically is the method for feedstock production hexahydroaniline with phenol.
Background technology
Hexahydroaniline (has another name called hexahydrophthalic anilide or aminocyclohexane; 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.The working method of hexahydroaniline mainly contains 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 is ripe, and raw material is easy to get, and selectivity is better, but the traditional processing technology of its raw materials used aniline can produce bigger pollution to environment, and production cost is higher, and remote effect are to the cost that with aniline is the hexahydroaniline that obtains of feedstock production.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 technical problem that the present invention will solve provides a kind of environmental protection, with low cost, method that operating procedure simply prepares hexahydroaniline.
For solving the problems of the technologies described above, contriver of the present invention has carried out a large amount of research and performing creative labour on the basis of existing technology, has developed a kind of preparation method of hexahydroaniline, and it is following that it specifically prepares process:
With phenol, H
2And NH
3Being raw material, is 150-260 ℃ in temperature of reaction, and reaction pressure is under 0.1～1Mpa, under the catalysis of palladium series catalyst, makes hexahydroaniline.
Described palladium series catalyst is Pd/ (Al
2O
3-MgO)/Al
2O
3, wherein the charge capacity of Pd is 0.05wt%～5wt%.
Said phenol: H
2: NH
3Mol ratio be 1: (5～15): (5～15).
Described palladium series catalyst Pd/ (Al
2O
3-MgO)/Al
2O
3The preparation method be, promptly to get with drying behind the magnesium-aluminium spinel carrier impregnation soluble palladium salts solution.
Described soluble palladium salts solution is PdCl
2Hydrochloric acid soln.
The preparation method of described magnesium-aluminium spinel carrier is with γ-Al
2O
3Dipping Mg (NO
3)
2And Al (NO
3)
3Mixing solutions, after the drying,, flood 1wt%～10wt%NaHCO then at 600～1400 ℃ of following roasting 2～6h
3The solution after drying promptly gets.
Said γ-Al
2O
3Mean pore size be 6-8nm.
Wherein the aperture should be greater than 80%～100% less than the pore volume ratio of the aperture of 10nm.
MgO: Al in the said magnesium-aluminium spinel carrier
2O
3Mol ratio be (1～4): 1.
Described catalyzer should be at 240-600 ℃ down with hydrogen activation 2-14 hour.
The present invention adopts the relatively cheap and preparation process of price not have the phenol of severe contamination to replace traditional raw material aniline, has both reduced the production cost of hexahydroaniline, can reduce the pollution to environment again.The preparation process of hexahydroaniline of the present invention can be inserted fixed-bed reactor with catalyzer, be heated to temperature of reaction after, feed phenol, hydrogen, ammonia by a certain percentage; Can react the generation hexahydroaniline; Therefore operating procedure of the present invention is simple, and the catalyst activity of the used palladium series catalyst of the present invention is high, and the life-span is long; The transformation efficiency of phenol is high, is not less than 90%; And the selectivity that generates hexahydroaniline is good, preferably can reach 89.4%.
Embodiment
Embodiment 1
Preparation magnesium-aluminium spinel carrier
With Mg (NO
3)
2And Al (NO
3)
3Be mixed with mixing solutions, this solution poured into γ-Al is housed
2O
3Beaker in, carry out incipient impregnation at twice; γ-Al wherein
2O
3Mean pore size be 7nm, the aperture is 89% less than the pore volume proportion of the aperture of 10nm.Descended dry 6 hours at 120 ℃ then, 900 ℃ of following roastings 6 hours, obtain magnesium-aluminium spinel after the cooling, wherein MgO: Al
2O
3Mol ratio be 3: 1; Then with resulting magnesium-aluminium spinel dipping 5wt%NaHCO
3Solution, dipping is back to be descended dry 6 hours at 120 ℃, promptly got.
The preparation catalyzer
With the above-mentioned magnesium-aluminium spinel carrier incipient impregnation PdCl that obtains
2Hydrochloric acid soln, drying obtains Pd/ (Al
2O
3-MgO)/Al
2O
3Catalyzer, wherein the charge capacity of Pd is 0.5wt%.
Deactivated catalyst
The above-mentioned catalyzer that makes under 300 ℃, is fed hydrogen catalyzer was carried out activation 10 hours.
The preparation hexahydroaniline
Behind the above-mentioned catalyst activation, feed phenol, hydrogen and ammonia, wherein the mol ratio of phenol and hydrogen, ammonia is 1: 10: 10, and temperature of reaction is 180 ℃, and reaction pressure is 0.1Mpa, and the transformation efficiency of phenol is 94.6%, and the selectivity of hexahydroaniline is 89.4%.
Embodiment 2
Preparation magnesium-aluminium spinel carrier
With Mg (NO
3)
2And Al (NO
3)
3Be mixed with mixing solutions, this solution poured into γ-Al is housed
2O
3Beaker in, carry out incipient impregnation at twice; γ-Al wherein
2O
3Mean pore size be 6nm, the aperture is 80% less than the pore volume proportion of the aperture of 10nm.Descended dry 4 hours at 110 ℃ then, 800 ℃ of following roastings 10 hours, obtain magnesium-aluminium spinel after the cooling, wherein MgO: Al
2O
3Mol ratio be 1: 1; Then with resulting magnesium-aluminium spinel dipping 1wt%NaHCO
3Solution, dipping is back to be descended dry 8 hours at 110 ℃, promptly got.
The preparation catalyzer
With the above-mentioned magnesium-aluminium spinel carrier incipient impregnation PdCl that obtains
2Hydrochloric acid soln, drying obtains Pd/ (Al
2O
3-MgO)/Al
2O
3Catalyzer, wherein the charge capacity of Pd is 0.2wt%.
Deactivated catalyst
The above-mentioned catalyzer that makes under 400 ℃, is fed hydrogen catalyzer was carried out activation 8 hours.
The preparation hexahydroaniline
Behind the above-mentioned catalyst activation, feed phenol, hydrogen and ammonia, wherein the mol ratio of phenol and hydrogen, ammonia is 1: 7: 12, and temperature of reaction is 190 ℃, and reaction pressure is 0.3Mpa, and the transformation efficiency of phenol is 93.1%, and the selectivity of hexahydroaniline is 76.5%.
Embodiment 3
Preparation magnesium-aluminium spinel carrier
With Mg (NO
3)
2And Al (NO
3)
3Be mixed with mixing solutions, this solution poured into γ-Al is housed
2O
3Beaker in, carry out incipient impregnation at twice; γ-Al wherein
2O
3Mean pore size be 8nm, the aperture is 98% less than the pore volume proportion of the aperture of 10nm.Descended dry 12 hours at 80 ℃ then, 1400 ℃ of following roastings 2 hours, obtain magnesium-aluminium spinel after the cooling, wherein MgO: Al
2O
3Mol ratio be 4: 1; Then with resulting magnesium-aluminium spinel dipping 10wt%NaHCO
3Solution, dipping is back to be descended dry 4 hours at 100 ℃, promptly got.
The preparation catalyzer
With the above-mentioned magnesium-aluminium spinel carrier incipient impregnation PdCl that obtains
2Hydrochloric acid soln, drying obtains Pd/ (Al
2O
3-MgO)/Al
2O
3Catalyzer, wherein the charge capacity of Pd is 0.05wt%.
Deactivated catalyst
The above-mentioned catalyzer that makes under 240 ℃, is fed hydrogen catalyzer was carried out activation 14 hours.
The preparation hexahydroaniline
Behind the above-mentioned catalyst activation, feed phenol, hydrogen and ammonia, wherein the mol ratio of phenol and hydrogen, ammonia is 1: 5: 5, and temperature of reaction is 150 ℃, and reaction pressure is 1Mpa, and the transformation efficiency of phenol is 92.3%, and the selectivity of hexahydroaniline is 67.5%.
Embodiment 4
Preparation magnesium-aluminium spinel carrier
With Mg (NO
3)
2And Al (NO
3)
3Be mixed with mixing solutions, this solution poured into γ-Al is housed
2O
3Beaker in, carry out incipient impregnation at twice; γ-Al wherein
2O
3Mean pore size be 6.5nm, the aperture is 85% less than the pore volume proportion of the aperture of 10nm.Descended dry 2 hours at 130 ℃ then, 600 ℃ of following roastings 8 hours, obtain magnesium-aluminium spinel after the cooling, wherein MgO: Al
2O
3Mol ratio be 3: 1; Then with resulting magnesium-aluminium spinel dipping 6wt%NaHCO
3Solution, dipping is back to be descended dry 10 hours at 80 ℃, promptly got.
The preparation catalyzer
With the above-mentioned magnesium-aluminium spinel carrier incipient impregnation PdCl that obtains
2Hydrochloric acid soln, drying obtains Pd/ (Al
2O
3-MgO)/Al
2O
3Catalyzer, wherein the charge capacity of Pd is 5wt%.
Deactivated catalyst
The above-mentioned catalyzer that makes under 550 ℃, is fed hydrogen catalyzer was carried out activation 2 hours.
The preparation hexahydroaniline
Behind the above-mentioned catalyst activation, feed phenol, hydrogen and ammonia, wherein the mol ratio of phenol and hydrogen, ammonia is 1: 15: 15, and temperature of reaction is 260 ℃, and reaction pressure is 0.5Mpa, and the transformation efficiency of phenol is 90.1%, and the selectivity of hexahydroaniline is 64.5%.
Embodiment 5
Preparation magnesium-aluminium spinel carrier
With Mg (NO
3)
2And Al (NO
3)
3Be mixed with mixing solutions, this solution poured into γ-Al is housed
2O
3Beaker in, carry out incipient impregnation at twice; γ-Al wherein
2O
3Mean pore size be 7.5nm, the aperture is 85% less than the pore volume proportion of the aperture of 10nm.Descended dry 3 hours at 110 ℃ then, 1200 ℃ of following roastings 7 hours, obtain magnesium-aluminium spinel after the cooling, wherein MgO: Al
2O
3Mol ratio be 2: 1; Then with resulting magnesium-aluminium spinel dipping 4wt%NaHCO
3Solution, dipping is back to be descended dry 2 hours at 140 ℃, promptly got.
The preparation catalyzer
With the above-mentioned magnesium-aluminium spinel carrier incipient impregnation PdCl that obtains
2Hydrochloric acid soln, drying obtains Pd/ (Al
2O
3-MgO)/Al
2O
3Catalyzer, wherein the charge capacity of Pd is 2wt%.
Deactivated catalyst
The above-mentioned catalyzer that makes under 350 ℃, is fed hydrogen catalyzer was carried out activation 9 hours.
The preparation hexahydroaniline
Behind the above-mentioned catalyst activation, feed phenol, hydrogen and ammonia, wherein the mol ratio of phenol and hydrogen, ammonia is 1: 10: 8, and temperature of reaction is 200 ℃, and reaction pressure is 0.2Mpa, and the transformation efficiency of phenol is 84.0%, and the selectivity of hexahydroaniline is 65.2%.
Claims (6)
1. the preparation method of a hexahydroaniline is characterized in that with phenol, H
2And NH
3Be raw material, phenol: H
2: NH
3Mol ratio be 1: (5～15): (5～15) are 150～190 ℃ in temperature of reaction, and reaction pressure is under 0.1～1Mpa, under the catalysis of palladium series catalyst, makes hexahydroaniline; Wherein, palladium series catalyst is Pd/ (Al
2O
3-MgO)/Al
2O
3, the charge capacity of Pd is 0.05wt%～5wt%, palladium series catalyst Pd/ (Al
2O
3-MgO)/Al
2O
3The preparation method be: with γ-Al
2O
3Dipping Mg (NO
3)
2And Al (NO
3)
3Mixing solutions, after the drying,, flood 1wt%～10wt%NaHCO then at 600～1400 ℃ of following roasting 2～10h
3The solution after drying obtains the magnesium-aluminium spinel carrier, with drying behind the magnesium-aluminium spinel carrier impregnation soluble palladium salts solution, promptly gets.
2. the preparation method of hexahydroaniline according to claim 1 is characterized in that described soluble palladium salts solution is PdCl
2Hydrochloric acid soln.
3. the preparation method of hexahydroaniline according to claim 1 is characterized in that said γ-Al
2O
3Mean pore size be 6～8nm.
4. the preparation method of hexahydroaniline according to claim 3 is characterized in that said γ-Al
2O
3Middle aperture is 80%～100% less than the pore volume proportion of the aperture of 10nm.
5. the preparation method of hexahydroaniline according to claim 1 and 2 is characterized in that MgO: Al in the said magnesium-aluminium spinel carrier
2O
3Mol ratio be (1～4): 1.
6. the preparation method of hexahydroaniline according to claim 1, it is characterized in that described catalyzer uses before, at 240-550 ℃ down with hydrogen activation 2-14 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710202742A CN101450903B (en) | 2007-11-28 | 2007-11-28 | Method for preparing cyclohexylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710202742A CN101450903B (en) | 2007-11-28 | 2007-11-28 | Method for preparing cyclohexylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101450903A CN101450903A (en) | 2009-06-10 |
| CN101450903B true CN101450903B (en) | 2012-09-05 |
Family
ID=40733406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710202742A Expired - Fee Related CN101450903B (en) | 2007-11-28 | 2007-11-28 | Method for preparing cyclohexylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101450903B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429155A (en) * | 1980-12-04 | 1984-01-31 | Basf Aktiengesellschaft | Preparation of aromatic amines |
-
2007
- 2007-11-28 CN CN200710202742A patent/CN101450903B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429155A (en) * | 1980-12-04 | 1984-01-31 | Basf Aktiengesellschaft | Preparation of aromatic amines |
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| Publication number | Publication date |
|---|---|
| CN101450903A (en) | 2009-06-10 |
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Owner name: HANERGY SOLAR PHOTOVOLTAIC TECHNOLOGY LIMITED Free format text: FORMER NAME: HANERGY TECHNOLOGY CO., LTD. |
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Address after: 100107 Beijing Chaoyang District Anli Road No. 0-A Patentee after: Hanenergy Solar Photovoltaic Technology Co.,Ltd Address before: 102209 Beijing city Changping District town Beiqijia Hongfu Pioneer Park No. 15 hospital Patentee before: Hanergy Technology Co., Ltd. |
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Granted publication date: 20120905 Termination date: 20191128 |