CN1231449C - Method of preparing adipinic acid using bionic catalytic oxggen to oxidize cyclohexane - Google Patents
Method of preparing adipinic acid using bionic catalytic oxggen to oxidize cyclohexane Download PDFInfo
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- CN1231449C CN1231449C CN 200310110349 CN200310110349A CN1231449C CN 1231449 C CN1231449 C CN 1231449C CN 200310110349 CN200310110349 CN 200310110349 CN 200310110349 A CN200310110349 A CN 200310110349A CN 1231449 C CN1231449 C CN 1231449C
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- hexanaphthene
- reaction
- hexanodioic acid
- oxygen
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 title abstract description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title abstract 8
- 229960000250 adipic acid Drugs 0.000 title 1
- 239000011664 nicotinic acid Substances 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 67
- 229910052760 oxygen Inorganic materials 0.000 claims description 52
- 239000001301 oxygen Substances 0.000 claims description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 50
- 239000000460 chlorine Substances 0.000 claims description 37
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000003624 transition metals Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- -1 nitro, hydroxyl Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 230000003647 oxidation Effects 0.000 abstract description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 102000004190 Enzymes Human genes 0.000 abstract description 3
- 108090000790 Enzymes Proteins 0.000 abstract description 3
- 235000011037 adipic acid Nutrition 0.000 abstract 3
- 239000001361 adipic acid Substances 0.000 abstract 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 235000001968 nicotinic acid Nutrition 0.000 abstract 1
- 239000000047 product Substances 0.000 description 92
- 239000007788 liquid Substances 0.000 description 47
- 238000004587 chromatography analysis Methods 0.000 description 46
- 238000012856 packing Methods 0.000 description 46
- 238000005303 weighing Methods 0.000 description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 9
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- FUTVBRXUIKZACV-UHFFFAOYSA-L zinc;3-[18-(2-carboxyethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,23-diid-2-yl]propanoic acid Chemical compound [Zn+2].[N-]1C(C=C2C(=C(C=C)C(C=C3C(=C(C=C)C(=C4)[N-]3)C)=N2)C)=C(C)C(CCC(O)=O)=C1C=C1C(CCC(O)=O)=C(C)C4=N1 FUTVBRXUIKZACV-UHFFFAOYSA-L 0.000 description 3
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- HGAHKUKYEGQDDR-UHFFFAOYSA-N [Fe].[Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].[Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 HGAHKUKYEGQDDR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 1
- 108010015742 Cytochrome P-450 Enzyme System Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The present invention relates to a method for preparing dicarboxylic acid, particularly to a method for preparing adipic acid by cyclohexane which is oxidized by bionics catalysis oxygen gas. The present invention takes metallic phthalocyanine with a similar structure as biologic enzyme and takes monocaryon metalloporphyrin or mu-oxygen-binuclear metalloporphyrin compounds as a catalyst, and the consumption of the catalyst is 0.01 to 0.1% of cyclohexane weight. The cyclohexane is used as a solvent, 0.5 to 3.5MPa oxygen gas is led in the solvent, reaction temperature is controlled at 110 to 160 DEG C, and reaction time is 4 to 32 h. The present invention has the advantages of little catalyst consumption, low reaction temperature and reaction pressure and easy oxidation depth control, and the catalyst has good catalytic performance for the adipic acid preparation reaction by the cyclohexane oxidized by the oxygen gas. The catalyst can be recycled for use, so preparation cost is low, the present invention adopts a one-step method to prepare the adipic acid, and the reaction has the advantage of simple and easy operation.
Description
Technical field
The present invention relates to a kind of preparation method of di-carboxylic acid, specifically, relate to the method that a kind of bionically catalyzing and oxidizing hexanaphthene prepares hexanodioic acid.
Background technology
One of method that at present prepares hexanodioic acid is hexanaphthene air-nitric acid oxidation method, and promptly under High Temperature High Pressure, hexanaphthene generates hexanodioic acid through nitric acid oxidation again through the mixture (KA oil) of atmospheric oxidation generation hexalin and pimelinketone.The shortcoming of this method is that equipment corrosion is serious, the energy consumption height, and complex operation, and also the second step nitric acid oxidation produces a large amount of NO
x, serious environment pollution.In order to overcome the shortcoming of two-step approach, have the people with the acetate of Co, Mn, Cu or the aluminium phosphate molecular sieve of Transition metal substituted (such as phosphorus Leyden blue CoAPO-5) as catalyzer, be solvent with acetic acid, prepare hexanodioic acid with air or oxygen direct oxidation hexanaphthene.Though this method has reduced the air pollution problems inherent that nitric acid oxidation brings, and has simplified operational condition, has improved conversion of cyclohexane, but still need to use the serious organic carboxyl acid of equipment corrosion, and energy consumption is higher as solvent.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operate, cost is low, do not have the method that corrosion and environment amenable bionically catalyzing and oxidizing hexanaphthene prepare hexanodioic acid.
The technical solution adopted in the present invention is: be raw material with the hexanaphthene, select any in the μ-oxygen-dinuclear metalloporphyrin of the monokaryon metalloporphyrin of metal phthalocyanine, general formula (II), (III) structure of general formula (I) structure or general formula (IV) structure for use as catalyzer, in the formula, M
1, M
2, M
3, M
4, M
5Be transition metal atoms, M
1=Fe, Co, Cu, Zn, M
2=Fe, Mn, Co, Cu, Zn, M
3=Fe, Mn, Co, M
4And M
5Can be identical, also can be different, when identical, M
4=M
5=Fe, Mn, Co, not simultaneously, M
4=Fe, M
5=Mn or M
4=Fe, M
5=Co, R can be that carboxyl also can be a hydrogen, R
1, R
2Can be hydrogen, halogen, nitro, hydroxyl, alkoxyl group, dentate X are chlorine, catalyst consumption is 0.1 of hexanaphthene weight～1 ‰, as solvent, feed the oxygen of 0.5～3.5MPa with hexanaphthene itself, control reaction temperature is 110～160 ℃, reaction times 4～32h, obtain the hexanodioic acid crude product, the employing ordinary method obtains the hexanodioic acid elaboration after separating, purifying.
Preferably have the monokaryon metalloporphyrin of general formula (III) structure or the μ-oxygen-dinuclear metalloporphyrin of general formula (IV) structure and make catalyzer.
Be preferably M in the general formula (III) especially
3=Mn or Fe, R
1=NO
2Or Cl, R
2=H, the monokaryon metalloporphyrin of X=Cl; M in the general formula (IV)
4=M
5=Fe or Mn or Co, M
4And M
5Not not simultaneously, M
4=Fe, M
5=Mn, R
1=NO
2Or Cl, R
2μ-oxygen of=H-dinuclear metalloporphyrin.
General formula (I)
General formula (II)
General formula (III)
General formula (IV)
The present invention is a catalyzer with metal phthalocyanine class and metal porphyrins, because it has and the identical core texture of some bio-oxidation enzyme (as oxygenase cytochrome P-450, oxyphorase, myohaemoglobin), thereby can be implemented in highly selective transmission under the mild conditions, activation oxygen molecule, and can the catalyzed oxidation organism.Especially the substituted metal porphyrin shows advantages of high catalytic activity and selectivity in catalytic oxidation, and need not consume reductive agent.The present invention just with metal phthalocyanine class and metal porphyrins as the agent of simulation biological enzyme, realized that under relatively mild condition the oxygen catalytic oxidation hexanaphthene prepares hexanodioic acid.Because catalyst levels is very little, temperature of reaction and reaction pressure are not high, so oxidation depth is easy to control.Structure and suitable adjusting process parameter by selecting catalyst can optionally obtain the oxidation products hexanodioic acid.Experimental results show that: these catalyzer all have good catalytic performance to the reaction that the dioxygen oxidation hexanaphthene prepares hexanodioic acid.In addition, the recyclable utilization of catalyzer reduces preparation cost.
The present invention can realize that solvent-freely oxidizing ethyle alkyl is produced hexanodioic acid.
The present invention adopts single stage method to make hexanodioic acid, simple, the easy row of operation.
Separate hexanodioic acid and only adopt the most basic decompress filter and recrystallization from the resulting reaction mixture of the present invention, can obtain highly purified hexanodioic acid, step is easy, and is easy to operate.
Embodiment
Embodiment 1
Taking by weighing 1mg four-(Chloro-O-Phenyl) iron porphyrin (is R in the general formula (II)
1=Cl, R
2=H, M
2=Fe), measure 15mL (11.7g) hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 140 ℃ of oil bath temperature controls, reaction 8h.Reaction mixture is realized solid-liquid separation through decompress filter, and liquid phase is inserted refrigerator internal cooling certain hour, separates out solid matter in solution, filter the back and merge with aforementioned solid, and recrystallization, drying is weighed.Detect with high pressure liquid chromatographic analysis, the yield that obtains hexanodioic acid is 18.2%, and the purity of the back product of purifying is 99.0%.
Embodiment 2
Taking by weighing 2mg four-(Chloro-O-Phenyl) cobalt porphyrin (is R in the general formula (II)
1=Cl, R
2=H, M
2=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 0.5MPa, 150 ℃ of oil bath temperature controls, reaction 12h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 6.9%, and the purity of the back product of purifying is 99.4%.
Embodiment 3
Taking by weighing 1mg four-(Chloro-O-Phenyl) manganoporphyrin (is R in the general formula (II)
1=Cl, R
2=H, M
2=Mn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 1.0MPa, 145 ℃ of oil bath temperature controls, reaction 10h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 8.6%, and the purity of the back product of purifying is 99.2%.
Embodiment 4
Taking by weighing 3mg four-(Chloro-O-Phenyl) copper porphyrin (is R in the general formula (II)
1=Cl, R
2=H, M
2=Cu), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 1.5MPa, 140 ℃ of oil bath temperature controls, reaction 11h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 6.2%, and the purity of the back product of purifying is 99.5%.
Embodiment 5
Taking by weighing 5mg four-(Chloro-O-Phenyl) zinc protoporphyrin (is R in the general formula (II)
1=Cl, R
2=H, M
2=Zn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 140 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 9.7%, and the purity of the back product of purifying is 98.9%.
Embodiment 6
Taking by weighing 3mg four-(rubigan) cobalt porphyrin (is R in the general formula (III)
1=H, R
2=Cl, M
2=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 140 ℃ of oil bath temperature controls, reaction 11h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 7.1%, and the purity of the back product of purifying is 99.3%.
Embodiment 7
Taking by weighing 7mg four-(rubigan) iron porphyrin (is R in the general formula (III)
1=H, R
2=Cl, M
2=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 130 ℃ of oil bath temperature controls, reaction 20h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 8.8%, and the purity of the back product of purifying is 99.0%.
Embodiment 8
Taking by weighing 3mg four-(rubigan) copper porphyrin (is R in the general formula (II)
1=H, R
2=Cl, M
2=Cu), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 145 ℃ of oil bath temperature controls, reaction 6h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 6.2%, and the purity of the back product of purifying is 99.3%.
Embodiment 9
Taking by weighing 2mg four-(rubigan) zinc protoporphyrin (is R in the general formula (II)
1=H, R
2=Cl, M
2=Zn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.5MPa, 135 ℃ of oil bath temperature controls, reaction 9h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 7.4%, and the purity of the back product of purifying is 99.1%.
Embodiment 10
Taking by weighing 5mg four-(o-methoxyphenyl) cobalt porphyrin (is R in the general formula (II)
1=OCH
3, R
2=H, M
2=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 140 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 9.0%, and the purity of the back product of purifying is 98.7%.
Embodiment 11
Taking by weighing 2mg four-(p-methoxyphenyl) cobalt porphyrin (is R in the general formula (II)
1=H, R
2=OCH
3, M
2=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 145 ℃ of oil bath temperature controls, reaction 4h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 6.5%, and the purity of the back product of purifying is 98.6%.
Embodiment 12
Taking by weighing 3mg four-(ortho-nitrophenyl base) manganoporphyrin (is R in the general formula (II)
1=NO
2, R
2=H, M
2=Mn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.5MPa, 140 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 15.4%, and the purity of the back product of purifying is 99.0%.
Embodiment 13
Taking by weighing 9mg four-(ortho-nitrophenyl base) copper porphyrin (is R in the general formula (II)
1=NO
2, R
2=H, M
2=Cu), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 140 ℃ of oil bath temperature controls, reaction 12h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 9.0%, and the purity of the back product of purifying is 99.3%.
Embodiment 14
Taking by weighing 3mg four-(ortho-nitrophenyl base) zinc protoporphyrin (is R in the general formula (II)
1=NO
2, R
2=H, M
2=Zn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 155 ℃ of oil bath temperature controls, reaction 16h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 18.0%, and the purity of the back product of purifying is 98.6%.
Embodiment 15
Taking by weighing 10mg four-(p-nitrophenyl) manganoporphyrin (is R in the general formula (II)
1=H, R
2=NO
2, M
2=Mn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 120 ℃ of oil bath temperature controls, reaction 14h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 7.3%, and the purity of the back product of purifying is 99.5%.
Embodiment 16
Taking by weighing 5mg four-(o-hydroxy-phenyl) iron porphyrin (is R in the general formula (II)
1=OH, R
2=H, M
2=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 110 ℃ of oil bath temperature controls, reaction 20h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 5.8%, and the purity of the back product of purifying is 99.1%.
Embodiment 17
Taking by weighing 2mg chlorination four-(Chloro-O-Phenyl) iron porphyrin (is R in the general formula (III)
1=Cl, R
2=H, M
3=Fe, X=Cl), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 140 ℃ of oil bath temperature controls, reaction 24h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 20.7%, and the purity of the back product of purifying is 99.3%.
Embodiment 18
Taking by weighing 1mg chlorination four-(Chloro-O-Phenyl) cobalt porphyrin (is R in the general formula (III)
1=Cl, R
2=H, M
3=Co, X=Cl), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.5MPa, 160 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 17.5%, and the purity of the back product of purifying is 99.4%.
Embodiment 19
Taking by weighing 3mg chlorination four-(Chloro-O-Phenyl) manganoporphyrin (is R in the general formula (III)
1=Cl, R
2=H, M
3=Mn, X=Cl), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 135 ℃ of oil bath temperature controls, reaction 28h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 19.2%, and the purity of the back product of purifying is 99.6%.
Embodiment 20
Taking by weighing 4mg chlorination four-(ortho-nitrophenyl base) iron porphyrin (is in the general formula (III)
R1=NO
2, R
2=H, M
3=Fe, X=Cl), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 1.5MPa, 155 ℃ of oil bath temperature controls, reaction 32h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 19.3%, and the purity of the back product of purifying is 99.2%.
Embodiment 21
Taking by weighing 1mg chlorination four-(ortho-nitrophenyl base) iron porphyrin (is R in the general formula (III)
1=NO
2, R
2=H, M
3=Fe, X=Cl), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.5MPa, 140 ℃ of oil bath temperature controls, reaction 12h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 19.5%, and the purity of the back product of purifying is 99.4%.
Embodiment 22
Taking by weighing 2mg chlorination four-(ortho-nitrophenyl base) manganoporphyrin (is R in the general formula (III)
1=NO
2, R
2=H, M
3=Mn, X=Cl), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 150 ℃ of oil bath temperature controls, reaction 16h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 19.9%, and the purity of the back product of purifying is 99.6%.
Embodiment 23
Taking by weighing 7mg chlorination four-(p-nitrophenyl) iron porphyrin (is R in the general formula (III)
1=H, R
2=NO
2, M
3=Fe X=Cl) is measured the 15mL hexanaphthene, and in the 200mL autoclave of packing into, aerating oxygen, pressure are 1.5MPa, 160 ℃ of oil bath temperature controls, reaction 9h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 13.0%, and the purity of the back product of purifying is 99.5%.
Embodiment 24
Taking by weighing 4mg chlorination four-(rubigan) manganoporphyrin (is R in the general formula (III)
1=H, R
2=Cl, M
3=Mn, X=Cl), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 155 ℃ of oil bath temperature controls, reaction 10h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 13.9%, and the purity of the back product of purifying is 99.1%.
Embodiment 25
Taking by weighing 2mg μ-oxygen-double-core four-(Chloro-O-Phenyl) iron porphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=M
5=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 140 ℃ of oil bath temperature controls, reaction 12h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 21.1%, and the purity of the back product of purifying is 99.5%.
Embodiment 26
Taking by weighing 7mg μ-oxygen-double-core four-(Chloro-O-Phenyl) iron porphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=M
5=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 140 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 19.9%, and the purity of the back product of purifying is 99.7%.
Embodiment 27
Taking by weighing 3mg μ-oxygen-double-core four-(Chloro-O-Phenyl) iron porphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=M
5=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.5MPa, 130 ℃ of oil bath temperature controls, reaction 10h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 16.8%, and the purity of the back product of purifying is 99.1%.
Embodiment 28
Taking by weighing 2mg μ-oxygen-double-core four-(Chloro-O-Phenyl) cobalt porphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=M
5=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 135 ℃ of oil bath temperature controls, reaction 14h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 18.5%, and the purity of the back product of purifying is 99.6%.
Embodiment 29
Taking by weighing 1mg μ-oxygen-double-core four-(Chloro-O-Phenyl) cobalt porphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=M
5=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 150 ℃ of oil bath temperature controls, reaction 6h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 14.2%, and the purity of the back product of purifying is 99.6%.
Embodiment 30
Taking by weighing 4mg μ-oxygen-double-core four-(Chloro-O-Phenyl) manganoporphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=M
5=Mn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 140 ℃ of oil bath temperature controls, reaction 16h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 18.3%, and the purity of the back product of purifying is 99.1%.
Embodiment 31
Taking by weighing 1mg μ-oxygen-double-core four-(ortho-nitrophenyl base) iron porphyrin (is R in the general formula (IV)
1=NO
2, R
2=H, M
4=M
5=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 145 ℃ of oil bath temperature controls, reaction 11h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 18.7%, and the purity of the back product of purifying is 99.5%.
Embodiment 32
Taking by weighing 2mg μ-oxygen-double-core four-(ortho-nitrophenyl base) cobalt porphyrin (is R in the general formula (IV)
1=NO
2, R
2=H, M
4=M
5=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 135 ℃ of oil bath temperature controls, reaction 14h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 18.2%, and the purity of the back product of purifying is 99.0%.
Embodiment 33
Taking by weighing 3mg μ-oxygen-double-core four-(p-nitrophenyl) iron porphyrin (is R in the general formula (IV)
1=H, R
2=NO
2, M
4=M
5=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.5MPa, 110 ℃ of oil bath temperature controls, reaction 20h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 12.5%, and the purity of the back product of purifying is 99.6%.
Embodiment 34
Taking by weighing 1mg μ-oxygen-double-core four-(ortho-nitrophenyl base) manganoporphyrin (is R in the general formula (IV)
1=NO
2, R
2=H, M
4=M
5=Mn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 140 ℃ of oil bath temperature controls, reaction 9h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 18.6%, and the purity of the back product of purifying is 99.3%.
Embodiment 35
Taking by weighing 1mg μ-oxygen-double-core four-(Chloro-O-Phenyl) iron-manganoporphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=Fe, M
5=Mn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.5MPa, 150 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 18.9%, and the purity of the back product of purifying is 99.2%.
Embodiment 36
Taking by weighing 2mg μ-oxygen-double-core four-(ortho-nitrophenyl base) iron-manganoporphyrin (is R in the general formula (IV)
1=NO
2, R
2=H, M
4=Fe, M
5=Mn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 160 ℃ of oil bath temperature controls, reaction 16h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 18.7%, and the purity of the back product of purifying is 99.7%.
Embodiment 37
Taking by weighing 5mg μ-oxygen-double-core four-(Chloro-O-Phenyl) iron-cobalt porphyrin (is R in the general formula (IV)
1=Cl, R
2=H, M
4=Fe, M
5=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 130 ℃ of oil bath temperature controls, reaction 24h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 13.8%, and the purity of the back product of purifying is 99.4%.
Embodiment 38
Taking by weighing 3mg μ-oxygen-double-core four-(ortho-nitrophenyl base) iron-cobalt porphyrin (is R in the general formula (IV)
1=NO
2, R
2=H, M
4=Fe, M
5=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 140 ℃ of oil bath temperature controls, reaction 10h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 14.5%, and the purity of the back product of purifying is 99.3%.
Embodiment 39
Take by weighing 5mg cobalt phthalocyanine (be R=H in the general formula (I), M
1=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 140 ℃ of oil bath temperature controls, reaction 16h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 9.6%, and the purity of the back product of purifying is 98.7%.
Embodiment 40
Take by weighing the 7mg iron-phthalocyanine (be R=H in the general formula (I), M
1=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 145 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 8.8%, and the purity of the back product of purifying is 98.6%.
Embodiment 41
Take by weighing the 9mg copper phthalocyanine (be R=H in the general formula (I), M
1=Cu), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 3.0MPa, 140 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 10.3%, and the purity of the back product of purifying is 98.5%.
Embodiment 42
Take by weighing 7mg zinc phthalocyanine (be R=H in the general formula (I), M
1=Zn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 150 ℃ of oil bath temperature controls, reaction 6h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 9.6%, and the purity of the back product of purifying is 98.7%.
Embodiment 43
Take by weighing 9mg tetracarboxylic cobalt phthalocyanine (be R=COOH in the general formula (I), M
1=Co), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 1.5MPa, 145 ℃ of oil bath temperature controls, reaction 12h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 7.2%, and the purity of the back product of purifying is 98.5%.
Embodiment 44
Take by weighing 3mg tetracarboxylic iron-phthalocyanine (be R=COOH in the general formula (I), M
1=Fe), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 155 ℃ of oil bath temperature controls, reaction 4h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 6.3%, and the purity of the back product of purifying is 98.7%.
Embodiment 45
Take by weighing 5mg tetracarboxylic copper phthalocyanine (be R=COOH in the general formula (I), M
1=Cu), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.0MPa, 130 ℃ of oil bath temperature controls, reaction 14h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 8.1%, and the purity of the back product of purifying is 98.8%.
Embodiment 46
Take by weighing 5mg tetracarboxylic zinc phthalocyanine (be R=COOH in the general formula (I), M
1=Zn), measure the 15mL hexanaphthene, in the 200mL autoclave of packing into, aerating oxygen, pressure are 2.5MPa, 135 ℃ of oil bath temperature controls, reaction 8h.Treatment step is with embodiment 1.Products obtained therefrom detects with high pressure liquid chromatographic analysis, and the yield that obtains hexanodioic acid is 7.9%, and the purity of the back product of purifying is 98.6%.
Claims (3)
1, a kind of bionically catalyzing and oxidizing hexanaphthene prepares the method for hexanodioic acid, it is characterized in that with the hexanaphthene being raw material, select any in the μ-oxygen-dinuclear metalloporphyrin of the monokaryon metalloporphyrin of metal phthalocyanine, general formula (II), (III) structure of (I) structure that has general formula or general formula (IV) structure for use as catalyzer, in the formula, M
1, M
2, M
3, M
4, M
5Be transition metal atoms, M
1=Fe, Co, Cu, Zn, M
2=Fe, Mn, Co, Cu, Zn, M
3=Fe, Mn, Co, M
4And M
5Can be identical, also can be different, when identical, M
4=M
5=Fe, Mn, Co, not simultaneously, M
4=Fe, M
5=Mn or M
4=Fe, M
5=Co, R are carboxyl or hydrogen, R
1, R
2Be hydrogen, halogen, nitro, hydroxyl or alkoxyl group, dentate X is a chlorine, catalyst consumption is 0.1 of hexanaphthene weight～1 ‰, as solvent, feed the oxygen of 0.5～3.5MPa with hexanaphthene itself, control reaction temperature is 110～160 ℃, reaction times 4～32h, obtain the hexanodioic acid crude product, the employing ordinary method obtains the hexanodioic acid elaboration after separating, purifying;
General formula (I)
General formula (II)
General formula (III)
General formula (IV)
2, bionically catalyzing and oxidizing hexanaphthene according to claim 1 prepares the method for hexanodioic acid, it is characterized in that selecting for use the monokaryon metalloporphyrin with general formula (III) structure or the μ-oxygen-dinuclear metalloporphyrin of general formula (IV) structure to make catalyzer.
3, bionically catalyzing and oxidizing hexanaphthene according to claim 1 and 2 prepares the method for hexanodioic acid, it is characterized in that described catalyzer is M in the general formula (III)
3=Mn or Fe, R
1=NO
2Or Cl, R
2M among the=H, the monokaryon metalloporphyrin of X=Cl or general formula (IV)
4=M
5=Fe or Mn or Co, M
4And M
5Not not simultaneously, M
4=Fe, M
5=Mn, R
1=NO
2Or Cl, R
2μ-oxygen of=H-dinuclear metalloporphyrin.
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| CN 200310110349 CN1231449C (en) | 2003-12-31 | 2003-12-31 | Method of preparing adipinic acid using bionic catalytic oxggen to oxidize cyclohexane |
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| FR2959741B1 (en) * | 2010-05-10 | 2014-11-07 | Rhodia Operations | PROCESS FOR THE PREPARATION OF CARBOXYLIC DIACIDS |
| CN103254060B (en) * | 2013-04-16 | 2015-04-15 | 衢州群颖化学科技有限公司 | Method for preparing adipic acid through co-catalytic oxidation of six-carbon oxygenated compound and cyclohexane |
| CN105665010B (en) * | 2014-11-20 | 2018-04-06 | 中国石油化工股份有限公司 | The catalyst of hexamethylene direct oxidation adipic acid |
| CN106083562A (en) * | 2016-06-09 | 2016-11-09 | 中山大学惠州研究院 | A kind of method that bionic catalysis n butane oxidation prepares acetic acid |
| CN109456174A (en) * | 2018-12-03 | 2019-03-12 | 浙江工业大学 | A kind of cyclooctane catalysis oxidation new method that reaction condition is mild |
| CN109456175A (en) * | 2018-12-03 | 2019-03-12 | 浙江工业大学 | A kind of cycloalkane catalysis oxidation new method that zinc protoporphyrin promotes |
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