CN1530358A - Catalyst oxdie cyclohexane process - Google Patents
Catalyst oxdie cyclohexane process Download PDFInfo
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- CN1530358A CN1530358A CNA2003101104584A CN200310110458A CN1530358A CN 1530358 A CN1530358 A CN 1530358A CN A2003101104584 A CNA2003101104584 A CN A2003101104584A CN 200310110458 A CN200310110458 A CN 200310110458A CN 1530358 A CN1530358 A CN 1530358A
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- oxidation
- pimelinketone
- hexalin
- hexanaphthene
- reaction
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims description 31
- 230000008569 process Effects 0.000 title claims description 13
- 239000003054 catalyst Substances 0.000 title abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 65
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 63
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims description 64
- 239000000047 product Substances 0.000 claims description 29
- 238000005516 engineering process Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- FYLJKQFMQFOLSZ-UHFFFAOYSA-N cyclohexylperoxycyclohexane Chemical compound C1CCCCC1OOC1CCCCC1 FYLJKQFMQFOLSZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000003809 water extraction Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 235000011037 adipic acid Nutrition 0.000 abstract description 3
- 239000001361 adipic acid Substances 0.000 abstract description 3
- 150000004032 porphyrins Chemical class 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- CVKFXBUVLBFHGO-UHFFFAOYSA-N cobalt 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Co].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 CVKFXBUVLBFHGO-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 8
- -1 cobalt salt Chemical class 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ODVRHJKVXOGKEJ-UHFFFAOYSA-N iron 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Fe].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 ODVRHJKVXOGKEJ-UHFFFAOYSA-N 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 3
- 108010015742 Cytochrome P-450 Enzyme System Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical class [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
A process for preparing cyclohexanol, cyclohexanone and adipic acid by catalytic oxidization of cyclohexane under existance of metallic porphyrin catalyst and a certain temp and pressure through combination of different reactors is disclosed. Its advantages are high single-pass conversion rate of cyclohexane and total output rate, low energy consumption and cost, and no need of cyclohexanol or acetone solvent and cocatalyst.
Description
Invention field
The present invention relates under the catalysis of metalloporphyrin effect, air oxidation of cyclohexane is produced hexalin, pimelinketone operational path, and air oxidation of cyclohexane is produced hexalin, pimelinketone, adipic acid route.
Background of invention
The pimelinketone industrial manufacture process mainly contains (one) phenol hydrogenation method in the world, (two) cyclohexane liquid-phase oxidation method, (three) cyclohexene hydration method.Present pimelinketone more than 90% is to adopt cyclohexane oxidation process to produce.The hexanaphthene direct oxidation process that has formed industrial technology 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.
(1) non-catalytic oxidation method
This method is one of main technique technology that adopts at present.Is cyclohexyl hydroperoxide with air (oxygen) with cyclohexane oxidation; Use Cobaltous diacetate (or other cobalt salt) to make catalyzer then, under alkaline condition, make cyclohexyl hydroperoxide be decomposed into hexalin and cyclohexanone mixture (being commonly called as KA oil).The cyclohexane conversion of this technology is 3-5% (mol), and the selectivity of hexalin and cyclohexanone mixture is about 80%.Be characterized in that the oxidizing process condition comparatively relaxes, the coking polymerization is less, and Technology is also ripe.But exist tangible deficiency: longer as operational path, the supplies consumption height pollutes big; The a large amount of spent lye treatment difficulties that particularly in the cyclohexyl hydroperoxide decomposition course, produce.
(2) boric acid is catalytic oxidation
This method is under the metaboric acid catalyst action, produces hexalin and pimelinketone with air (oxygen) direct oxidation hexanaphthene; The hexanaphthene per pass conversion reaches at 3.6% o'clock, generates the selectivity higher (91.6%) (JP 63222132A2, on September 16th, 1988) of hexalin and pimelinketone.The deadly defect of this technology is: recovery boric acid in service is very complicated, and the Financial cost height has increased the consumption of a large amount of general facilitiess, and the serious obstruction of equipment that boric acid catalyst is easy to cause and pipeline has influenced this The Application of Technology and development.
(3) cobalt salt catalytic oxidation
This method is that cobalt salts such as employing cobalt naphthenate, cobalt stearate, cobalt oleate, cobalt octoate, cobalt naphthenate chromium complexes are catalyzer, produce hexalin and pimelinketone with air (oxygen) direct oxidation hexanaphthene, this process at first is that hexanaphthene and oxygen form cyclohexyl hydroperoxide by free radical reaction, this superoxide decomposes under catalyst action generates pimelinketone, hexalin then.The hexalin, the pimelinketone that produce are easy to oxidized generation carboxylic acid, ester, in order to reduce the generation of by product, improve the selectivity and the yield of pimelinketone, hexalin, must control conversion of cyclohexane, and the residence time of product.Cyclohexane conversion generally is controlled at about 5%, the residence time is less than 50min, its advantage is the reaction conditions gentleness, temperature is about 160 ℃, about pressure 1.1Mpa, the residence time is short, and equipment requirements is low, and plant factor is higher, cyclohexane conversion can reach 6%, hexalin, the selectivity of pimelinketone is about 80%, but the carboxylic acid that produces in this reaction process is easy and catalyst reaction, generate the carboxylic acid cobalt salt, remain on equipment and the pipeline, slagging scorification blocking pipe and valve reduce the device driving cycle, and hexalin, the selectivity of pimelinketone is lower, and consumption is increased.
Hexalin, pimelinketone technology exist all that cyclohexane conversion is low because the cyclohexane oxidation of present industrial application is produced, hexalin, problem that the pimelinketone selectivity is low, 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 engineering portion 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, the bubbling air reaction is 4 hours in the mixture of hexanaphthene, acetylacetonate cobalt and N-hydroxyphthalimide, the yield of pimelinketone reach 89% (WO 2000048975A1,2000-08-24); If the reaction times is 2 hours, cyclohexane conversion is 11%, and the hexalin selectivity is 49%, the pimelinketone selectivity reach 40% (JP2000239210A2,2000-09-05).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, the synthetic difficulty of this compound costs an arm and a leg; Catalyzer passes through processes such as filtration, extraction, hydrolysis, saponification, distillation or rectifying, separating technology complexity with additive with the needs that separate of reaction system.
The many organism of cytochrome P-450 energy catalysis in the Living organism are by molecular oxygen oxidation, fatty compounds hydroxylation etc. for example, be unique enzyme that can make the hydrocarbon polymer functionalization in the life entity, cytochrome P-450 list oxygenation enzyme catalysis hydrocarbon polymer hydroxylating has specificity, highly selective.From 1979, Groves etc. have proposed iodosobenzene---metalloporphyrin---hexanaphthene simulated system, realized manual simulation's reaction of cytochrome P-450 list oxygenation enzyme first, the catalysis of metalloporphyrin oxidizing ethyle alkyl that people have synthesized many types generates hexalin, but generally be confined to simulate life condition (normal temperature, normal pressure), its result of study is difficult to be applied to industrialization.1992, disclose the method for an a kind of adjustable step catalysis synthesizing cyclohexanol, pimelinketone, hexanodioic acid among the CN1062718A of Liu Shangchang etc., it is characterized in that the organic high conductivity polymer molecular clustering of transition metal catalyzer is applied to the hexanaphthene is in the production technique of initial feed synthesizing cyclohexanol, pimelinketone, hexanodioic acid.Wherein at tetraphenylporphyrin cobalt concentration 2 * 10
-2M～10
-4M, 149 ℃～160 ℃ of temperature of reaction, 1.5 hours reaction times, reaction pressure 0.5Mpa, the mol ratio of hexanaphthene and hexalin or acetone is 6: 1 in the coupling solvent, cyclohexane conversion reaches 54%, pimelinketone selectivity 95%.At tetraphenylporphyrin concentration of iron 2 * 10
-2M～10
-4M, 145 ℃～155 ℃ of temperature of reaction, 3.6 hours reaction times, reaction pressure 0.7Mpa, the mol ratio of hexanaphthene and hexalin or acetone is 3: 7 in the coupling solvent, cyclohexane conversion reaches 60%, hexanodioic acid selectivity 95%.2000, the method of catalytic air oxidation alkane and naphthenic hydrocarbon is disclosed among the CN1116258C of Guo Cancheng etc., be to select for use monometallic porphyrin or μ-oxygen bimetallic porphyrin to make Primary Catalysts, 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 for 95%.
Summary of the invention
The object of the present invention is to provide a kind ofly under the catalysis of metalloporphyrin effect, air oxidation of cyclohexane is produced the catalyzed oxidation hexanaphthene technology of hexalin and pimelinketone, makes conversion of cyclohexane reach 5%～12%, and yield reaches more than 88%.Relate to a kind ofly under the catalysis of metalloporphyrin effect, air oxidation of cyclohexane is produced the catalyzed oxidation hexanaphthene technology of hexalin, pimelinketone, hexanodioic acid, makes conversion of cyclohexane reach 5～15%, and yield reaches more than 90%.
The objective of the invention is to realize in the following manner:
1, under the metalloporphyrin effect, the temperature and pressure that control is fit to, the direct catalyzed oxidation liquid phase of air hexanaphthene, generate hexalin, pimelinketone, cyclohexyl peroxide, organic acid and organic acid acetic, the hexanaphthene that oxidized tail gas is taken out of reclaims by the heat recovery system condensation, and be back to each oxidation reactor according to temperature of reaction, oxidation products is under alkalescence and metal-salt catalytic condition, make cyclohexyl peroxide be decomposed into hexalin and pimelinketone, after separating, organic phase makes most hexanaphthenes be circulated to oxidation system again by the hexanaphthene Distallation systm, and product enters pimelinketone and hexalin distillation system, obtains effective product pimelinketone and hexalin.Perhaps oxidation products is through after the heat exchange, and with organic acid in the process water extraction oxidation products, water is by concentrated, crystallization, centrifugation, and filter cake is the hexanodioic acid that reclaims, and the water of evaporation and a small amount of organism are circulated to extraction.Organic phase is under alkalescence and cobalt salt catalytic condition, the cyclohexyl peroxide selectivity that oxidation is produced is decomposed into hexalin, pimelinketone, after separating, organic phase makes most hexanaphthenes be circulated to oxidation system again by the hexanaphthene Distallation systm, product enters pimelinketone and hexalin distillation system, obtains effective product pimelinketone and hexalin.
2, air oxidation of cyclohexane is produced hexalin, the pimelinketone operational path is under the condition that the catalysis of metalloporphyrin agent exists, control catalyst concentration 0.5～6mg/l.125～150 ℃ of temperature of reaction, reaction pressure 0.8～1.2Mpa makes hexanaphthene carry out oxidation in liquid phase with air.Reactor types comprises slot type ((circulation) bubbling style, whirlpool contact, stirring-type, outer circulation type that downtake is arranged), tower (bubble tower, shell and tube, tray column, mechanical stirring bubble tower) etc.Reactor is one or several series, parallel or series-parallel connection.Reaction time is 30～90min, and oxygen concentration remains in the safety margin in the reacted tail gas.Oxidation products is through after the heat exchange, and under alkalescence and cobalt salt catalytic condition, the cyclohexyl peroxide selectivity is decomposed into hexalin, pimelinketone.After separating, organic phase makes most hexanaphthenes be circulated to oxidation system again by the hexanaphthene Distallation systm, and product enters pimelinketone and hexalin distillation system, obtains effective product pimelinketone and hexalin.
3, air oxidation of cyclohexane production hexalin, pimelinketone, adipic acid route are under the condition that the catalysis of metalloporphyrin agent exists, control catalyst concentration 0.5～6mg/l.125～150 ℃ of temperature of reaction, reaction pressure 0.8～1.2Mpa makes hexanaphthene carry out oxidation in liquid phase with air.Reactor types comprises slot type ((circulation) bubbling style, whirlpool contact, stirring-type, outer circulation type that downtake is arranged), tower (bubble tower, shell and tube, tray column, mechanical stirring bubble tower) etc., and reactor is one or several series, parallel or series-parallel connection.Reaction times is 30～90min, and oxygen concentration remains in the safety margin in the reacted tail gas.Oxidation products is through after the heat exchange, and temperature is reduced to 70～140 ℃, organic acid in the process water extraction oxidation products of adding 2%～20%.Water is by concentrating, and concentrated solution is 0～30 ℃ of crystallization, centrifugation, and the hexanodioic acid of filter cake for reclaiming, the water of evaporation and a small amount of organism are circulated to extraction.Organic phase is under alkalescence and cobalt salt catalytic condition, and the cyclohexyl peroxide selectivity that oxidation is produced is decomposed into hexalin, pimelinketone.After separating, organic phase makes most hexanaphthenes be circulated to oxidation system again by the hexanaphthene Distallation systm, and product enters pimelinketone and hexalin distillation system, obtains effective product pimelinketone and hexalin.
The present invention's advantage and positively effect compared with prior art is:
Air oxidation of cyclohexane is produced hexalin and pimelinketone technology and the existing hexanaphthene liquid-phase air oxidation technology of using relatively among the present invention, and its remarkable advantage: 1, hexanaphthene per pass conversion and total recovery improve simultaneously, can reach 10% and 88% respectively.Under identical pimelinketone output, it is nearly 50% that the internal circulating load of hexanaphthene can reduce, and alleviates the load of hexanaphthene Distallation systm, cuts down the consumption of energy and manufacturing cost.2, this technology can directly apply to existing cyclohexane oxidation full scale plant, reaches the purpose that reduces production costs and expand energy.3, this technology has also been avoided the hexalin or the acetone solvent that are adopted among the CN1062718A, has avoided the transition metal salt or the oxide compound co-catalyst that are adopted among the CN1116258C, has novelty.4, the concentration of this technology catalysis of metalloporphyrin agent in system minimum (1～6mg/l), be applied to industrial production, very little to the influence of the manufacturing cost of product.
Embodiment:
Embodiment 1 is at three 0.4M
3In the oxidation reactor, process flow sheet is seen accompanying drawing 1, and oxidation reactor is three placed in-line band mechanical stirring reactors, and the cyclohexane feed amount keeps 1M
3/ per hour, under the catalysis of metalloporphyrin effect, air is added by reactor bottom, reaction pressure 0.9Mpa, and the hexanaphthene that oxidized tail gas is taken out of reclaims by condensation, is back to reactor.Oxidation products is cooled to 85 ℃, sends into a 0.4M
3Be with in the churned mechanically reactor, organism mixes with alkali, basicity is controlled at 1.0mg/meq, acid in the organism and alkali reaction generate organic acid sodium salt, and the ester type organic is decomposed into organic acid and pure type organic, temperature of reactor is controlled at 90 ℃, pressure-controlling, is separated the inorganics in the organism by the alkali separating tank at 0.3MPa.In the hexanaphthene water distilling apparatus, reclaim hexanaphthene, obtain thick hexalin and cyclohexanone mixture.Testing data sees Table 1.
Table 1
| Sequence number | Catalyzer | Catalyst concn ppm | Temperature of reaction ℃ | Transformation efficiency % | Hexalin and pimelinketone selectivity % |
| ??1 | The tetraphenylporphyrin cobalt | ????2.5 | ??145～148 | ????7.2 | ????90 |
| ??2 | The tetraphenylporphyrin cobalt | ????3 | ??146～150 | ????10 | ????88.50 |
| ??3 | Tetraphenylporphyrin iron | ????4 | ??146～150 | ????9.5 | ????90 |
| ??4 | Tetraphenylporphyrin iron | ????3.5 | ??146～148 | ????8 | ????91 |
Embodiment 2 is in a 80L bubbling column reactor, and the cyclohexane feed amount per hour keeps 100L/, under this catalyst action, air is added by reactor bottom, air is oxidizing ethyle alkyl under 0.9MPa pressure, and the hexanaphthene that oxidized tail gas is taken out of reclaims by condensation, is back to reactor.
Table 2
| Sequence number | Catalyzer | Catalyst concn ppm | Temperature of reaction ℃ | Transformation efficiency % | Hexalin and pimelinketone and mistake selectivity % |
| 1 | The tetraphenylporphyrin cobalt | ????2.5 | ??145～148 | ????7.6 | ????90 |
| 2 | The tetraphenylporphyrin cobalt | ????3 | ??147～151 | ????9.8 | ????88.60 |
| 3 | Tetraphenylporphyrin iron | ????4 | ??148～151 | ????9.3 | ????90.2 |
| ????4 | Tetraphenylporphyrin iron | ????3.5 | ??148～150 | ????7.5 | ????91.5 |
Embodiment 3 is in a 100L shell and tube reactor, and the cyclohexane feed amount per hour keeps 100L/, and the content of tetraphenylporphyrin cobalt catalyst is 2.5mg/l in the hexanaphthene, and air is added by reactor bottom; Under this catalyst action, air is oxidizing ethyle alkyl under 148 ℃, 0.9MPa pressure, and the molar yield of hexanaphthene is 6.8%; The hexanaphthene that oxidized tail gas is taken out of reclaims by condensation, is back to reactor.The selectivity of hexalin, pimelinketone and cyclohexyl hydroperoxide is 92% in the oxidation products, and wherein cyclohexyl hydroperoxide accounts for 20%.
Embodiment 4 is at 5 45M
3In the oxidation reactor, reactor is 5 placed in-line built-in diversing bucket reactors, the cyclohexane feed amount keep 100 tons/per hour, the content of tetraphenylporphyrin cobalt catalyst is 2.5mg/l in the hexanaphthene, air is added by reactor bottom; Under this catalyst action, air is oxidizing ethyle alkyl under 145 ℃～148 ℃, 0.9MPa pressure, and the hexanaphthene that oxidized tail gas is taken out of reclaims by condensation, is back to reactor.The molar yield of hexanaphthene is 7.6%, and the selectivity of hexalin, pimelinketone and cyclohexyl hydroperoxide is 90.5% in the oxidation products, and wherein cyclohexyl hydroperoxide accounts for 17%.
Embodiment 5 is at three 0.4M
3In the oxidation reactor, oxidation reactor is three placed in-line band mechanical stirring reactors, and the cyclohexane feed amount keeps 1M
3/ per hour, the content of tetraphenylporphyrin cobalt catalyst is 4mg/l in the hexanaphthene, air is added by reactor bottom; Under this catalyst action, air is oxidizing ethyle alkyl under 155 ℃, 0.95MPa pressure, and the time is 75 minutes, and the hexanaphthene that oxidized tail gas is taken out of reclaims by condensation, is back to reactor.The molar yield of hexanaphthene is 15%; Oxidation products is through after the heat exchange, and temperature is reduced to 70～140 ℃, organic acid in the process water extraction oxidation products of adding 5%.Water is by concentrating, and concentrated solution is 0～30 ℃ of crystallization, centrifugation, and the hexanodioic acid of filter cake for reclaiming, the water that evaporates and a small amount of organism are circulated to extraction.0.4M of organic phase
3Be with in the churned mechanically reactor, organism mixes with alkali, basicity is controlled at 1.0mg/meq, acid in the organism and alkali reaction generate organic acid sodium salt, and the ester type organic is decomposed into organic acid and pure type organic, temperature of reactor is controlled at 90 ℃, pressure-controlling, is separated the inorganics in the organism by the alkali separating tank at 0.3MPa.In the hexanaphthene water distilling apparatus, reclaim hexanaphthene, in hexalin, pimelinketone rectifier unit, make with extra care out pimelinketone and hexalin, in the cyclohexanol dehydrogenation device hexalin is converted into pimelinketone, the total recovery of hexanodioic acid, pimelinketone is 93%, hexanodioic acid: pimelinketone is 1: 3.5.
Claims (5)
1. catalyzed oxidation hexanaphthene technology, it is characterized in that, under the metalloporphyrin effect, the temperature and pressure that control is fit to, the direct catalyzed oxidation liquid phase of air hexanaphthene, generate hexalin, pimelinketone, cyclohexyl peroxide, organic acid and organic acid acetic, the hexanaphthene that oxidized tail gas is taken out of reclaims by the heat recovery system condensation, and be back to each oxidation reactor according to temperature of reaction, oxidation products is under alkalescence and metal-salt catalytic condition, make cyclohexyl peroxide be decomposed into hexalin and pimelinketone, after separating, organic phase makes most hexanaphthenes be circulated to oxidation system again by the hexanaphthene Distallation systm, product enters pimelinketone and hexalin distillation system, obtain effective product pimelinketone and hexalin, perhaps oxidation products is through after the heat exchange, with organic acid in the process water extraction oxidation products, water is by concentrating, crystallization, centrifugation, the hexanodioic acid of filter cake for reclaiming, the water of evaporation and a small amount of organism are circulated to extraction, organic phase is under alkalescence and cobalt salt catalytic condition, the cyclohexyl peroxide selectivity that oxidation is produced is decomposed into hexalin, pimelinketone, after separating, organic phase makes most hexanaphthenes be circulated to oxidation system again by the hexanaphthene Distallation systm, product enters pimelinketone and hexalin distillation system, obtains effective product pimelinketone and hexalin.
2. according to the method for claim 1, it is characterized in that the catalysis of metalloporphyrin agent concentration is 0.5～6mg/l.
3. according to the method for claim 1, it is characterized in that oxidizing reaction temperature is 125～150 ℃, reaction pressure is 0.8～1.2Mpa, and reaction time is 30～90min.
4. according to the method for claim 1, it is characterized in that the oxidation reactor form comprises slot type ((circulation) bubbling style, whirlpool contact, stirring-type, outer circulation type that downtake is arranged), tower (bubble tower, shell and tube, tray column, mechanical stirring bubble tower) etc.Reactor is one or several series, parallel or series-parallel connection.
5. according to the method for claim 1, it is characterized in that oxidation products is through after the heat exchange, temperature is reduced to 70～140 ℃, adds 2%～20% process water extraction, and extraction back water concentrated solution extracts hexanodioic acid 0～30 ℃ of crystallization.
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| WO2007134521A1 (en) * | 2006-05-22 | 2007-11-29 | Hunan University | Apparatus and technology for preparing cyclohexanol, cyclohexanone and adipic acid by air oxidization of cyclohexane |
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