CN100445255C - Method for catalytic hydrogenation of six carbocyclic compound by schiff bases-porphyrin metallic compound - Google Patents
Method for catalytic hydrogenation of six carbocyclic compound by schiff bases-porphyrin metallic compound Download PDFInfo
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- CN100445255C CN100445255C CNB2007101027478A CN200710102747A CN100445255C CN 100445255 C CN100445255 C CN 100445255C CN B2007101027478 A CNB2007101027478 A CN B2007101027478A CN 200710102747 A CN200710102747 A CN 200710102747A CN 100445255 C CN100445255 C CN 100445255C
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Abstract
The invention discloses a catalyzing and oxidizing method of C6-ring compound through schiff bases-porphyrin metal compound, which comprises the following steps: controlling reacting temperature after aerating air or oxygen; allocating solid carrier as catalyst with structural formula compound or compound and organic and inorganic macromolecule through physical or chemical method; manufacturing KA oil or adipic acid or selecting structural formula compound or their solid carrier as main catalyst and transition metal salt or oxide as co-catalyst.
Description
Technical field
The present invention relates to a kind of method of schiff bases-porphyrin metallic compound catalyzed oxidation hydrogenation of six carbocyclic compound.
Background technology
KA oil, hexanodioic acid all are the important source material in the fine chemistry industry.At present, the production method of industrial KA oil mainly adopts cyclohexane oxidation process production, and industrial production hexanaphthene direct oxidation process mainly contains three kinds of methods: i.e. non-catalytic oxidation method, boric acid class catalytic oxidation and soluble metal salt catalyst homogeneous oxidizing method.But these methods all exist reaction conditions harsh relatively, and cyclohexane conversion is low, the low problem of KA oil selectivity, so development environment close friend's inexpensive, low temperature, high-selectivity catalyst are the main development trends of research.
The Japan Hirai Naruhisa professor of Kansai University invention, the N-hydroxyphthalimide catalytic oxidation of your (Daicel) chemical industrial company exploitation of contest, it is catalyzer that this technology adopts N-hydroxyphthalimide and acetylacetonate cobalt mixture, in temperature of reaction is 160 ℃, 4.0MPa down, bubbling air reaction is 4 hours in the mixture of hexanaphthene, acetylacetonate cobalt and N-hydroxyphthalimide, the pimelinketone yield reach 89% (WO2000048975A1,2004-08-24); If the reaction times is 2 hours, cyclohexane conversion is 11%, and the hexalin selectivity is 49%, the pimelinketone selectivity reach 40% (JP200239210A2,2000-09-05).But the catalyzer organometallic compound acetylacetonate cobalt large usage quantity that this technology adopts (hexanaphthene quality 6.79%), need simultaneously to add a large amount of additive N-hydroxyphthalimide (hexanaphthene quality 17%) in the reaction system, this compound with become the difficulty, cost an arm and a leg; The discrete of catalyzer and additive and reaction system needs through processes such as filtration, extraction, hydrolysis, saponification, distillation or rectifying, separating technology complexity.
2000, the method of catalytic air oxidation alkane and naphthenic hydrocarbon is disclosed among the CN1116258C of Guo Cancheng etc., be to select to make Primary Catalysts with monometallic porphyrin or bimetallic porphyrin, the consumption of Primary Catalysts is 40～200ppm, make co-catalyst with transition metal salt or oxide compound, the mol ratio of Primary Catalysts and co-catalyst is 1: 3～5.Feeding the 1atm air, temperature is under 25～150 ℃ of conditions, cyclohexane conversion 4～8%, and hexalin and pimelinketone selectivity are 95%.
2003, catalyzed oxidation hexanaphthene technology is disclosed among the CN1530358 of Xiao Junqin etc., under its processing condition, the porphyrin consumption is 0.5-6mg/L, oxidizing reaction temperature is 125-150 ℃, reaction pressure is 0.8-1.2MPa, and reaction time is 30-90min, and conversion of cyclohexane can reach 10%.
Hexanodioic acid is to have most in the aliphatic dibasic acid to use part-time diprotic acid, is important Organic Chemicals.The main method of present industrial production hexanodioic acid is a nitric acid oxidation method, promptly generates hexanodioic acid with nitric acid oxidation KA oil.This method shortcoming is that equipment corrosion is serious, energy consumption height, complex operation, the NO that is produced in this course
X, environment is caused serious pollution.
2004, the CN1535947A of Guo Cancheng etc. disclosed the method for atmospheric oxidation hydrogenation of six carbocyclic compound hexanodioic acid.Under the 1-20atm air conditions, temperature of reaction is 50-200 ℃, select for use bimetallic porphyrin and monometallic porphyrin or their immobilized thing to make Primary Catalysts, make co-catalyst with transition metal salt or oxide compound, catalyst concn is 1-100PPM, hydrogenation of six carbocyclic conversion of compounds rate is between 5-70%, and the selectivity of product hexanodioic acid is between 50-90%.
2004, the method that the bionically catalyzing and oxidizing hexanaphthene of She Yuanbin etc. prepares hexanodioic acid discloses, select for use with the metalphthelein mountain valley with clumps of trees and bamboo, monokaryon metalloporphyrin or the dinuclear metalloporphyrin compounds of biological enzyme structural similitude and make catalyzer, consumption is the 0.1-1 ‰ of hexanaphthene quality, oxygen pressure is 0.5-3.5MPa, temperature of reaction is 110-160 ℃, reaction times 4-32 hour.Adipic acid yield is up to 20.7%.
Summary of the invention
The objective of the invention is to utilize a kind of brand-new bionic catalyst to the hydrogenation of six carbocyclic compound, as hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene or their mixture etc., under the oxidation of air or oxygen,, change needed oxidation products effectively into by the reacting condition condition.This catalyst levels is little, and cost is low, the catalytic efficiency height; Reaction conditions relaxes, hydrogenation of six carbocyclic compound ratio transformation height.
The method of schiff bases-porphyrin metallic compound catalyzed oxidation hydrogenation of six carbocyclic compound of the present invention, press routine step and carry out:
A, under 1-40atm air or oxygen condition, temperature of reaction is 30-180 ℃, the reaction times is 0.5-10 hour;
B, select for use schiff bases-porphyrin compound or compound and inorganic and organic polymer to make catalyzer separately by the immobilized thing that physics or chemical process constitute, or select for use schiff bases-porphyrin compound or compound and inorganic and organic polymer to make Primary Catalysts by the immobilized thing that physics or chemical process constitute, Primary Catalysts account for 100,000 of hydrogenation of six carbocyclic compound quality/to ten thousand/, make co-catalyst with transition metal salt or oxide compound, structural formula is:
The atoms metal M in the structure wherein
1, M
2, be transition metal atoms; Substituent R on the phenyl ring
1-R
7Be hydrogen or alkyl or alkoxyl group or hydroxyl or halogen or amido or amino or replacement glycosyl and cyclodextrin; Dentate X is acetate or methyl ethyl diketone or halogen or pyridine or pyrroles.
Co-catalyst is 8 with the ratio of Primary Catalysts amount: 1-3: 1.
Described hydrogenation of six carbocyclic compound is hexanaphthene or hexalin or pimelinketone or tetrahydrobenzene.
Described hydrogenation of six carbocyclic compound is the hexalin of different ratios and the mixture of pimelinketone.
Described immobilized title complex is to be made of title complex and carrier: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene.
The transition metal salt of described co-catalyst or oxide compound are the salt or the oxide compound of metal: Cu, Zn, Fe, Co, Mn, Cr, Ni.
The present invention is feeding under 1～40atm air or oxygen condition, 30～180 ℃ of control reaction temperature, select for use the immobilized thing that constitutes by physics or chemical process by the compound of above-mentioned general formula or above-claimed cpd and inorganic and organic polymer separately as catalyzer, catalyst levels account for 100,000 of hydrogenation of six carbocyclic compound quality/to ten thousand/, realize that air or oxygen produces KA oil or hexanodioic acid to the oxidation of different hydrogenation of six carbocyclic raw materials of compound.
Also can select for use by the compound of structural formula or their immobilized thing as Primary Catalysts, with transition metal salt or oxide compound as co-catalyst, the Primary Catalysts consumption account for 100,000 of hydrogenation of six carbocyclic compound quality/to ten thousand/, the Primary Catalysts ratio of catalyst substance amount together is 1: 3-1: 8, realize that air or oxygen generates KA oil or hexanodioic acid to the oxidation of different hydrogenation of six carbocyclic raw materials of compound.
Employed hydrogenation of six carbocyclic compound is hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene among the present invention, also can be the hexalin of different ratios and the mixture of pimelinketone.
The composite catalyst that schiff bases-porphyrin metallic compound of the present invention or they and transition metal and oxide compound constitute the results showed, the reaction that the mixture that air or oxygen oxidizing ethyle alkyl and tetrahydrobenzene are generated KA oil and hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene or hexalin and pimelinketone generates hexanodioic acid has good catalytic performance.With the variation of reactant condition, hexanaphthene and tetrahydrobenzene are generated as the transformation efficiency of KA oil between 4-70%, and the selectivity of product KA oil is between 80-96%; The mixture of hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene or hexalin and pimelinketone generates the transformation efficiency of hexanodioic acid between 4-80%, and the selectivity of product hexanodioic acid is between 60-95%.
Embodiment
Embodiment 1
15mg had the compound of structural formula, R
1=R
2=R
3=R
4=R
5=R
6=R
7=H, M
1=M
2=Fe, X are the pyrroles, and Y=Cl adds in the 300mL hexanaphthene, feeds the 10atm air, and 140 ℃ of following stirring reactions 2 hours, cyclohexane conversion was 18%, and KA oil selectivity accounts for 85% in the reactant.
Embodiment 2
10mg had the compound of structural formula, R
1=R
2=R
4=H, R
3=Cl, R
5=R
6=R
7=H, M
1=M
2=Mn, X=Cl, Y are pyridine, and polyvinyl chloride particles is a carrier, adds in the 300mL hexanaphthene, feeds 10atm oxygen, and 140 ℃ of following stirring reactions 4 hours, cyclohexane conversion was 25%, and KA oil selectivity accounts for 62% in the reactant.
Embodiment 3
15mg had the compound of structural formula, R
1=R
3=CH
3, R
2=R
4=H, R
5=R
6=R
7=Cl, M
1=M
2=Co, molecular sieve is a carrier, adds in the 300mL tetrahydrobenzene, feeds the 2atm air, and 135 ℃ of following stirring reactions 3 hours, the tetrahydrobenzene transformation efficiency was 75%, and KA oil selectivity accounts for 85% in the reactant.
Embodiment 4
10mg had the compound of structural formula, R
1=R
3=Cl, R
2=R
4=H, R
5=R
6=R
7=H, M
1=Mn, M
2=Fe, X=Y=Br, zeolite are carrier, add in the 300mL hexanaphthene, feed 10atm oxygen, and 140 ℃ of following stirring reactions 4 hours, cyclohexane conversion was 25%, and KA oil selectivity accounts for 65% in the reactant.
Embodiment 5
15mg had the compound of structural formula, R
1=R
3=R
5=R
6=R
7=Cl, R
2=R
4=H, M
1=M
2=Mn, X=Cl add in the 300mL hexanaphthene, feed 20atm oxygen, and 140 ℃ of following stirring reactions 4 hours, cyclohexane conversion was 36%, and KA oil selectivity accounts for 11.8% in the reactant.
Embodiment 6
30mg had the compound of structural formula, R
1=R
2=R
3=R
4=CH
3, R
5=R
6=R
7=Cl, M
1=Ni, M
2=Mn, Y=Br, polystyrene are carrier, add in the 300mL tetrahydrobenzene, feed the 40atm air, and 145 ℃ of following stirring reactions 6 hours, cyclohexane conversion was 41%, and KA oil selectivity accounts for 11.9% in the reactant.
Embodiment 7
10mg had the compound of structural formula, R
1=R
3=NO
3, R
2=R
4=H, R
5=R
6=R
7=NH
2, M
1=Fe, M
2=Co, polyvinyl chloride particle are carrier, add in the 300mL tetrahydrobenzene, feed 30atm oxygen, and 150 ℃ of following stirring reactions 4 hours, cyclohexane conversion was 45%, and KA oil selectivity accounts for 12.7% in the reactant.
Embodiment 8
3mg had the compound of structural formula, R
1, R
3For replacing glycosyl, R
2=R
4=H, R
5=R
6=H, R
7=OH, M
1=Zn, M
2=Cu, X are acetate, and Y is a pyridine, and sepiolite is a carrier, and 18mgCuCl
2Add together in the 400mL hexanaphthene, feed 10atm oxygen, 110 ℃ of following stirring reactions 5 hours, cyclohexane conversion was 2.1%, and KA oil selectivity accounts for 95%.
Embodiment 9
5mg had the compound of structural formula, R
1=R
3=OCH
3, R
2=R
4=R
5=H, R
6=R
7=Cl, M
1=Ni, M
2=Mn, molecular sieve is a carrier, adds in each mixed solution of 50% of 300mL hexalin and pimelinketone, feeds the 10atm air, 135 ℃ of following stirring reactions 8 hours, adipic acid yield 97%.
Embodiment 10
30mg had the compound of structural formula, R
1=R
2=R
3=R
4=R
5=R
6=R
7=H, M
1=M
2=Cu, X=Y=Cl, polyvinyl chloride particle are carrier, add in the 300mL hexanaphthene, feed 25atm oxygen, and 120 ℃ of following stirring reactions 10 hours, cyclohexane conversion was 26%, and KA oil selectivity accounts for 8.5% in the reactant.
Embodiment 11
15mg had the compound of structural formula, R
1=R
3=R
7=NH
2, R
2=R
4=R
5=R
6=H, M
1=Zn, M
2=Cu, porous ceramics are carrier, and 35mgFeCl
2Add in the 400mL hexalin, feed 5atm oxygen, 80 ℃ of following stirring reactions 3 hours, the hexalin transformation efficiency was 81%, and adipic acid yield is 85%.
Embodiment 12
8mg had the compound of structural formula, R
1=R
2=R
3=R
4=H, R
5=R
6=R
7=CH
3, M
1=Mn, M
2=Co, X=Y=Cl, zeolite are carrier, and 20mgCuCl
2Add in the 200mL pimelinketone, feed the 6atm air, 70 ℃ of following stirring reactions 5 hours, the pimelinketone transformation efficiency was 83%, and adipic acid yield is 91%.
Embodiment 13
15mg had the compound of structural formula, R
1=R
2=R
3=R
4=CH
3, R
5=R
6=H, R
7=Br, M
1=M
2=Co, molecular sieve is a carrier, and 35mgMnCl
2Add in the 300mL hexanaphthene, feed 15atm oxygen, 130 ℃ of following stirring reactions 3 hours, cyclohexane conversion was 8%, and adipic acid yield is 3%.
Embodiment 14
30mg had the compound of structural formula, R
1=R
3=OCH
3, R
2=R
4=R
5=R
6=H, R
7=NH
2, M
1=M
2=Ni, X=Cl, Y are pyridine and 60mgFeSO
4Add in the 300mL hexanaphthene, feed 15atm oxygen, 180 ℃ of following stirring reactions 2 hours, cyclohexane conversion was 43%, and adipic acid yield is 18%.
Embodiment 15
4mg had the compound of structural formula, R
1=R
3=R
7=OH, R
1=R
4=R
5=R
6=H, M
1=Fe, M
2=Ni, X=Br, granules of polystyrene are carrier, and 15mgZnCl
2Add in the 200mL tetrahydrobenzene, feed 1atm oxygen, 30 ℃ of following stirring reactions 0.5 hour, cyclohexane conversion was 72%, and adipic acid yield is 25%.
Claims (6)
1, a kind of method of schiff bases-porphyrin metallic compound catalyzed oxidation hydrogenation of six carbocyclic compound is characterized in that pressing routine step and carries out:
A, under 1-40atm air or oxygen condition, temperature of reaction is 30-180 ℃, the reaction times is 0.5-10 hour;
B, select for use schiff bases-porphyrin compound or compound and inorganic and organic polymer to make catalyzer separately by the immobilized thing that physics or chemical process constitute, or select for use schiff bases-porphyrin compound or compound and inorganic and organic polymer to make Primary Catalysts by the immobilized thing that physics or chemical process constitute, Primary Catalysts account for 100,000 of hydrogenation of six carbocyclic compound quality/to ten thousand/, make co-catalyst with transition metal salt or oxide compound, structural formula is:
The atoms metal M in the structure wherein
1Be Cu, Zn, Fe, Co, Mn, Ni, M
2Be transition metal atoms Cu, Fe, Co, Mn, Ni; Substituent R on the phenyl ring
1-R
7Be hydrogen or methyl or methoxy or hydroxyl or halogen or amido; Dentate X is acetate or methyl ethyl diketone or halogen or pyridine or pyrroles.
2, method according to claim 1 is characterized in that the co-catalyst and the ratio of Primary Catalysts amount are 8: 1-3: 1.
3, method according to claim 1 is characterized in that described hydrogenation of six carbocyclic compound is hexanaphthene or hexalin or pimelinketone or tetrahydrobenzene.
4,, it is characterized in that described hydrogenation of six carbocyclic compound is the hexalin of different ratios and the mixture of pimelinketone according to the described method of claim 1.
5,, it is characterized in that described immobilized title complex is made of title complex and a kind of carrier that is selected from down group: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene according to the described method of claim 1.
6,, it is characterized in that the transition metal salt of described co-catalyst or oxide compound are salt or the oxide compound that is selected from down a kind of metal of group: Cu, Zn, Fe, Co, Mn, Ni according to the described method of claim 1.
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| CNB2007101027478A CN100445255C (en) | 2007-04-21 | 2007-04-21 | Method for catalytic hydrogenation of six carbocyclic compound by schiff bases-porphyrin metallic compound |
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| CN100445255C true CN100445255C (en) | 2008-12-24 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191218C (en) * | 2002-10-29 | 2005-03-02 | 湖南大学 | Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin |
| CN1218922C (en) * | 2003-04-08 | 2005-09-14 | 湖南大学 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
| CN1234709C (en) * | 2002-07-29 | 2006-01-04 | 山东理工大学 | Biporphin metal coordination compound with bridge linking face-face structure and its use |
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2007
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234709C (en) * | 2002-07-29 | 2006-01-04 | 山东理工大学 | Biporphin metal coordination compound with bridge linking face-face structure and its use |
| CN1191218C (en) * | 2002-10-29 | 2005-03-02 | 湖南大学 | Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin |
| CN1218922C (en) * | 2003-04-08 | 2005-09-14 | 湖南大学 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
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