CN103965033B - The method of pimelinketone is prepared in a kind of catalysis of phenol selective hydrogenation - Google Patents
The method of pimelinketone is prepared in a kind of catalysis of phenol selective hydrogenation Download PDFInfo
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- CN103965033B CN103965033B CN201410209634.8A CN201410209634A CN103965033B CN 103965033 B CN103965033 B CN 103965033B CN 201410209634 A CN201410209634 A CN 201410209634A CN 103965033 B CN103965033 B CN 103965033B
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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Abstract
The method of pimelinketone is prepared in a kind of catalysis of phenol selective hydrogenation, it is characterized in that adopting Pd/C-heteropolyacid composite catalyst system to be catalyzer, be 1: 0.1 ~ 1: 20 at Pd/C and heteropolyacid mass ratio, phenol and composite catalyst system mass ratio are 50: 3 ~ 100: 1, the solvent that phenol quality is 1 ~ 5 times, temperature of reaction 40 ~ 100 DEG C, reacts 1.0 ~ 4.0h and prepares pimelinketone, and recycle and reuse catalyst system under the condition of hydrogen pressure 0.5 ~ 2.0MPa.Compared with prior art: 1. catalyst system has efficient catalytic activity and selectivity.2. product postprocessing is simple.3. namely can be used for reaction next time without any process after catalyst reaction, and catalytic performance has no reduction, recycles performance good.
Description
Technical field
The present invention relates to a kind of method that pimelinketone is prepared in catalysis of phenol selective hydrogenation, namely relate to the novel method that pimelinketone is prepared in the selective hydrogenation of a kind of Pd/C-heteropolyacid composite catalyst system catalysis of phenol.
Background technology
Pimelinketone is a kind of important industrial chemicals, is the important intermediate of synthetic nylon-6 and nylon-66, is also widely used in coating, fuel, medicine and other fields.Along with China's chemical fiber industry develop rapidly, the output of hexanolactam increases year by year, and the demand of raw material pimelinketone is huge, has a extensive future.The production technique of pimelinketone mainly contains cyclohexane oxidation process, cyclohexene hydration method, benzene hydrogenation method, cyclohexanol method, phenol hydrogenation method.Compared with other techniques, phenol hydrogenation method has the advantages such as production operation safety, reaction conditions is gentle, product separation is purified conveniently, technical process is short.At present, phenol shortening multiplex Pd, Ru, Cu, Yt, Ni, Pt even load type catalyzer, but under these catalysts, phenol is easy to hydrogenation and directly generates hexalin, causes phenol selectivity Hydrogenation for the inefficiency of pimelinketone.Therefore, research and develop new selective hydrogenation catalyst and become a problem important and urgently to be resolved hurrily.
Heteropolyacid is by different oxygen acid condensations and the general name of obtained condensation oxygen acid, and having very high catalytic activity and oxidation-reduction quality, is a kind of multi-functional catalytic material.Compared with traditional catalyst, it has the internal structure determined, unique false liquid phase reaction field, in polar solvent, have the advantages such as good solubility.In organic catalytic reaction, heteropoly compound demonstrates higher catalytic activity and selectivity.Due to its in the reaction low to the corrodibility of equipment, reaction conditions is gentle, is therefore subject to extensive concern in recent years.The present invention proposes to adopt the selective hydrogenation of Pd/C-heteropolyacid composite catalyst system catalysis of phenol to prepare the novel method of pimelinketone thus.
Summary of the invention
Pimelinketone is prepared in the eco-friendly composite catalyst catalysis of phenol selective hydrogenation that the object of the invention is to propose a kind of catalytic performance excellent, effectively can improve the selectivity of pimelinketone and the recovery repeat performance of catalyst system.
The present invention relates to a kind of method that pimelinketone is prepared in catalysis of phenol selective hydrogenation, it is characterized in that adopting Pd/C-heteropolyacid composite catalyst system to be catalyzer, be 1: 0.1 ~ 1: 20 at Pd/C and heteropolyacid mass ratio, phenol and composite catalyst system mass ratio are 50: 3 ~ 100: 1, the solvent that phenol quality is 1 ~ 5 times, temperature of reaction 40 ~ 100 DEG C, reacts 1.0 ~ 4.0h and prepares pimelinketone, and recycle and reuse catalyst system under the condition of hydrogen pressure 0.5 ~ 2.0MPa.
The present invention is characterized in that described Pd/C-heteropolyacid composite catalyst system, wherein the one of Pd/C to be Pd massfraction be 5% or 10%, and heteropolyacid is the one in phospho-wolframic acid, silicotungstic acid or phospho-molybdic acid.
The present invention is characterized in that described solvent is the one in trichloromethane, methylene dichloride, tetrahydrofuran (THF) or hexanaphthene.
The present invention is characterized in that described reaction conditions with Pd/C (Pd mass percent 5%) and heteropolyacid mass ratio for 1: 1 ~ 1: 10, phenol and composite catalyst system mass ratio are 50: 2 ~ 100: 2, the dichloromethane solvent that phenol quality is 2 ~ 3 times, temperature of reaction 70 ~ 90 DEG C, hydrogen pressure 1.0 ~ 1.5MPa, reaction times 2.0 ~ 3.0h are good.
The present invention solves this technical problem by the following technical programs:
For phenol hydrogenation preparing cyclohexanone, concrete technical scheme is described.
1. typical case's preparation of pair pimelinketone is for catalyzer (Pd/C and heteropolyacid mass ratio 1: 1 ~ 1: 10) with Pd/C-heteropolyacid composite catalyst system, phenol and composite catalyst system mass ratio are 50: 2 ~ 100: 2, the dichloromethane solvent that phenol quality is 2 ~ 3 times, dropping into is furnished with in the autoclave of magnetic agitation, thermocouple thermometer, be filled with 1.0 ~ 1.5MPa hydrogen, heated and stirred reaction 2.0 ~ 3.0h at temperature of reaction 70 ~ 90 DEG C.Cool to room temperature after reaction, centrifugal, get supernatant liquid, remove solvent and obtain product pimelinketone.
2. the catalyzer that uses of method of the present invention is reusable, because catalyst system can be deposited in the bottom of reaction solution after centrifugal.Namely lower catalyst system can be used for lower catalytic hydrogenation reaction without the need to any process, reuses 5 times, and catalytic performance has no obvious decline.
The present invention, compared with conventional catalyst technique, is characterized in:
1. catalyzer has efficient catalytic activity and selectivity.
2. product postprocessing is simple, and gained by product is few.
3. namely can be used for reaction next time without any process after catalyst reaction, and catalytic performance has no reduction, recycles performance good.
Specific implementation method
Being described further method of the present invention below in conjunction with embodiment, is not limitation of the invention.
Embodiment 1: (wherein in Pd/C, the massfraction of Pd is 5% by 10g phenol, 0.3gPd/C-phospho-wolframic acid, the mass ratio 1: 5 of Pd/C and phospho-wolframic acid) and 20g methylene dichloride add in stainless steel autoclave, air in hydrogen exchange still, then 1.0MPa hydrogen is filled with, heated and stirred 3h at 80 DEG C, leaves standstill and is cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 100%, and pimelinketone selectivity is 93.6%.
Comparative example 1: add in stainless steel autoclave by 10g phenol, 0.3gPd/C (wherein in Pd/C, the massfraction of Pd is 5%) and 20g methylene dichloride, air in hydrogen exchange still, then be filled with 1.0MPa hydrogen, heated and stirred 3h at 80 DEG C, leave standstill and be cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 61.2%, and pimelinketone selectivity is 59.6%.
Comparative example 2: add in stainless steel autoclave by 10g phenol, 0.3g phospho-wolframic acid and 20g methylene dichloride, air in hydrogen exchange still, be then filled with 1.0MPa hydrogen, heated and stirred 3h at 80 DEG C, leave standstill and are cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 0%, and pimelinketone selectivity is 0%.
Comparative example 3: add in stainless steel autoclave by 10g phenol, 0.3gRaneyNi and 20g methylene dichloride, air in hydrogen exchange still, is then filled with 1.0MPa hydrogen, heated and stirred 3h at 80 DEG C, leave standstill and are cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 89.3%, and pimelinketone selectivity is 40.1%.
Comparative example 4: by 10g phenol, 0.3gPd/C-ZnCl
2(wherein in Pd/C, the massfraction of Pd is 5%, Pd/C and ZnCl
2mass ratio 1: 5) and 20g trichloromethane add in stainless steel autoclave, air in hydrogen exchange still, is then filled with 1.0MPa hydrogen, heated and stirred 3h at 80 DEG C, leave standstill be cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 100%, and pimelinketone selectivity is 69.3%.
Comparative example 5: collect the catalyzer in above-mentioned example and comparative example respectively, reusability investigation is carried out under identical experiment condition, experimental result shows: Pd/C-phospho-wolframic acid composite catalyst system reuses 5 times, the transformation efficiency of phenol is 97.7%, and the selectivity of pimelinketone is 92.3%.RaneyNi reuses 3 times, and the transformation efficiency of phenol is 65.2%, and the selectivity of pimelinketone is 54.3%.Pd/C-ZnCl
2composite catalyst system reuses 3 times, and the transformation efficiency of phenol is 88.8%, and the selectivity of pimelinketone is 67.5%.
Embodiment 2: (wherein in Pd/C, the massfraction of Pd is 10% by 10g phenol, 0.6gPd/C-phospho-molybdic acid, the mass ratio 1: 0.1 of Pd/C and phospho-molybdic acid) and 10g tetrahydrofuran (THF) add in stainless steel autoclave, air in hydrogen exchange still, then 0.5MPa hydrogen is filled with, heated and stirred 4h at 40 DEG C, leaves standstill and is cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 78.6%, and pimelinketone selectivity is 86.6%.
Embodiment 3: (wherein in Pd/C, the massfraction of Pd is 10% by 10g phenol, 1.0gPd/C-silicotungstic acid, the mass ratio 1: 20 of Pd/C and silicotungstic acid) and 50g hexanaphthene add in stainless steel autoclave, air in hydrogen exchange still, then 2.0MPa hydrogen is filled with, heated and stirred 1h at 100 DEG C, leaves standstill and is cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 100%, and pimelinketone selectivity is 92.3%.
Embodiment 4: (wherein in Pd/C, the massfraction of Pd is 10% by 10g phenol, 0.3gPd/C-silicotungstic acid, the mass ratio 1: 7 of Pd/C and silicotungstic acid) and 30g methylene dichloride add in stainless steel autoclave, air in hydrogen exchange still, then 1.5MPa hydrogen is filled with, heated and stirred 2h at 90 DEG C, leaves standstill and is cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 100%, and pimelinketone selectivity is 95.3%.
Embodiment 5: (wherein in Pd/C, the massfraction of Pd is 5% by 10g phenol, 0.4gPd/C-phospho-wolframic acid, the mass ratio 1: 10 of Pd/C and phospho-wolframic acid) and 25g hexanaphthene add in stainless steel autoclave, air in hydrogen exchange still, then 1.0MPa hydrogen is filled with, heated and stirred 2h at 70 DEG C, leaves standstill and is cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 90.5%, and pimelinketone selectivity is 89.8%.
Embodiment 6: (wherein in Pd/C, the massfraction of Pd is 10% by 10g phenol, 0.5gPd/C-phospho-molybdic acid, the mass ratio 1: 0.5 of Pd/C and phospho-molybdic acid) and 30g trichloromethane add in stainless steel autoclave, air in hydrogen exchange still, then 1.5MPa hydrogen is filled with, heated and stirred 3h at 90 DEG C, leaves standstill and is cooled to room temperature.By still liquid centrifuging and taking supernatant liquid, the catalyzer after centrifugal, can be directly used in lower secondary response.Phenol conversion is 100%, and pimelinketone selectivity is 85.7%.
Claims (3)
1. the method for pimelinketone is prepared in a catalysis of phenol selective hydrogenation, it is characterized in that adopting Pd/C-heteropolyacid composite catalyst system to be catalyzer, be 1: 0.1 ~ 1: 20 at Pd/C and heteropolyacid mass ratio, phenol and composite catalyst system mass ratio are 50: 3 ~ 100: 1, the solvent that phenol quality is 1 ~ 5 times, temperature of reaction 40 ~ 100 DEG C, reacts 1.0 ~ 4.0h and prepares pimelinketone, and recycle and reuse catalyst system under the condition of hydrogen pressure 0.5 ~ 2.0MPa; Described heteropolyacid is the one in phospho-wolframic acid, silicotungstic acid or phospho-molybdic acid; Described solvent is the one in trichloromethane, methylene dichloride, tetrahydrofuran (THF) or hexanaphthene.
2. preparation method as claimed in claim 1, is characterized in that described Pd/C-heteropolyacid composite catalyst system, wherein the one of Pd/C to be Pd massfraction be 5% or 10%.
3. preparation method as claimed in claim 1, it is characterized in that described reaction conditions with Pd/C and heteropolyacid mass ratio for 1: 1 ~ 1: 10, phenol and composite catalyst system mass ratio are 50: 2 ~ 100: 2, the dichloromethane solvent that phenol quality is 2 ~ 3 times, temperature of reaction 70 ~ 90 DEG C, hydrogen pressure 1.0 ~ 1.5MPa, reaction times 2.0 ~ 3.0h are good.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3076810A (en) * | 1960-06-15 | 1963-02-05 | Allied Chem | Process for the production of cyclohexanone |
| CN101709027A (en) * | 2009-11-27 | 2010-05-19 | 中国科学院化学研究所 | Method and special catalyst for preparing cyclohexanone in one step by phenol hydrogenation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3076810A (en) * | 1960-06-15 | 1963-02-05 | Allied Chem | Process for the production of cyclohexanone |
| CN101709027A (en) * | 2009-11-27 | 2010-05-19 | 中国科学院化学研究所 | Method and special catalyst for preparing cyclohexanone in one step by phenol hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| "载体对钯催化剂催化苯酚加氢制环己酮性能的影响";朱俊华等;《催化学报》;20070531;第28卷(第5期);441-445 * |
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Address after: No.8 Xingyu Road, Rongcheng City, Weihai City, Shandong Province, 264300 Patentee after: QING MU HIGH-TECH MATERIALS Co.,Ltd. Address before: 264300 south of Rongchang Road, Rongcheng City, Weihai City, Shandong Province Patentee before: RONGCHENG QING MU HIGH-TECH MATERIALS Co.,Ltd. |