CN100363317C - Method for preparing cyclohexanone and cyclohexanol by cyclohexane oxidation - Google Patents
Method for preparing cyclohexanone and cyclohexanol by cyclohexane oxidation Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 152
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 230000003647 oxidation Effects 0.000 title claims abstract description 147
- 238000000034 method Methods 0.000 title claims abstract description 50
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical group OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims abstract description 23
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- -1 transition metal salt Chemical class 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 33
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229930194542 Keto Natural products 0.000 claims description 3
- WIRUZQNBHNAMAB-UHFFFAOYSA-N benzene;cyclohexane Chemical compound C1CCCCC1.C1=CC=CC=C1 WIRUZQNBHNAMAB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000007172 homogeneous catalysis Methods 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- JBSWPCUWUNTVKK-UHFFFAOYSA-N OC(C)=C(C(CC)(CC)P(O)(O)=O)CCCC Chemical group OC(C)=C(C(CC)(CC)P(O)(O)=O)CCCC JBSWPCUWUNTVKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
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- 150000003839 salts Chemical class 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 abstract 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
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- 239000001488 sodium phosphate Substances 0.000 description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 9
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 9
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for preparing cyclohexanone and cyclohexanol by cyclohexane oxidation, which is characterized in that when cyclohexane oxidation reaction starts, 0.005 to 100 ppm of soluble transitional metal salts as catalysts are added to cyclohexane; simultaneously, 0.1 to 10 ppm of accumulated bis-phosphonic acid ester as a precipitation inhibitor is added to the cyclohexane; the production is carried out for 1 to 24 hours by adopting a cyclohexane catalytic oxidation method; after cyclohexane oxidation reaction is normal, the transitional metal salts as catalysts is immediately stopped to be added to the cyclohexane in an oxidation reactor, but 0.05 to 1 ppm of accumulated bis-phosphonic acid ester is continuously added to the cyclohexane in the oxidation reactor all the time. Thus, the accumulated bis-phosphonic acid ester can be used as a passivating agent of trace metal ions which are carried on materials and a metal wall of the oxidation reactor. The decomposition of cyclohexyl hydrogen peroxide in the oxidation reactor is reduced, and the production is carried out for a long time by adopting a cyclohexane non-catalytic method. Thereby, the safety production starting from oxidation and the high producing yield of devices are ensured.
Description
The present invention relates to the modification method that a kind of cyclohexane oxidation prepares pimelinketone and hexalin.
(1), under pressure 0.8～2.0Mpa condition,, generates the oxidation liquid mixture that contains pimelinketone, hexalin and cyclohexyl hydroperoxide with the gas cyaniding hexanaphthene of molecule-containing keto 140～200 ℃ of temperature;
(2) 50～170 ℃ of temperature, under pressure 0.001～2.0Mpa condition, carry out the homogeneous catalysis decomposition or in alkaline aqueous solution, carry out non-even phase decomposition with the oil soluble transition-metal catalyst, make the cyclohexyl hydroperoxide in the oxidation liquid mixture decompose generation pimelinketone and hexalin with transition-metal catalyst;
(3) with rectifying tower separating benzene-cyclohexane, pimelinketone and hexalin; Above cyclohexane oxidation prepares the method for pimelinketone and hexalin, can be from ZL88105772.X, and ZL94110939.9, ZL98112730.4, US5233092A is known in the JP2067789 patent documentation.
As everyone knows, known cyclohexane oxidation processing method mainly is divided into hexanaphthene cobalt salt catalytic oxidation and two kinds of operational paths of hexanaphthene non-catalyst oxidation method.Hexanaphthene cobalt salt catalytic oxidation operational path is that E.I.Du Pont Company is in the last century invention fifties, through updating over 50 years, Technology is quite ripe, become the most classical industrial process of cyclohexane oxidation, many world-class major companies are still adopting hexanaphthene cobalt salt catalytic oxidation to produce pimelinketone and hexalin at present, the great advantage of hexanaphthene cobalt salt catalytic oxidation is that oxidation pressure is low, be 0.8～1.0Mpa, temperature is low, and 140～160 ℃, speed of response is fast, reacting balance safety, especially before oxidizing reaction begins, owing to added cobalt naphthenate, perhaps cobalt octoate, Cobalt Porphyrin, chromium naphthenate, transition-metal catalysts such as chromic acid tert-butyl, these transition metal ions and radical have isolobal analogy, just equal before oxidizing reaction begins, in hexanaphthene, added " radical ", thereby when cyclohexane oxidation begins, eliminated or shortened decomposition induction time; Pressurized air just can enter normal reaction speed after feeding very soon, and the oxygen level in the oxidized tail gas does not raise, and has guaranteed the steady safety that cyclohexane oxidation is produced.But hexanaphthene catalytic oxidation yield is low, and the adding of transition metal ion, and having generated is the slagging scorification precipitation of core with the transition metal salt, and these slagging scorification occluding device and pipelines make the continuous production cycle below six months; The invention of diphosphonate ester and application have reached more than 1 year the hexanaphthene catalyzed oxidation production cycle, the industrial production of a plurality of factories proves, adopt the transition metal-catalyzed oxidation style of hexanaphthene to add the diphosphonate ester of 0.05～1ppm simultaneously, after the continuous production 1 year, do not clean, open oxidation reactor, find that wall and corresponding pipeline still keep stainless steel equipment gloss, very clean, some slagging scorification do not have yet.Though the slagging scorification problem of the transition metal-catalyzed oxidation of hexanaphthene has solved, the problem that the yield of hexanaphthene catalytic oxidation is low does not solve.
In order to solve the technical barrier of the low and slagging scorification of hexanaphthene catalytic oxidation yield, developed hexanaphthene non-catalyst oxidation method the seventies in last century, over nearly 30 years, newly-built cyclohexane oxidation factory mostly adopts hexanaphthene non-catalyst oxidation method operational path to produce.The characteristics of hexanaphthene non-catalyst oxidation method are exactly, and during oxidation begins to carry out with oxidation, do not have the existence of transition-metal catalyst in the material of oxidation reactor.Therefore hexanaphthene non-catalyst oxidation method needs higher pressure, be 1.1～2.0Mpa, higher temperature, it is 165～200 ℃, only under the pressure and temperature higher than hexanaphthene catalytic oxidation, hexanaphthene non-catalyst oxidation method could guarantee certain oxidizing reaction speed, thereby guarantees the index about 2% of the residue Control for Oxygen Content of oxidized tail gas in safety.Oxidation reactor metal wall once had patent report to the catalytic decomposition of cyclohexyl hydroperoxide under the high temperature in order to eliminate, and with trisodium phosphate passive oxidation reactor wall, perhaps added the micro-octyl phosphate or the trisodium phosphate aqueous solution to oxidation reactor continuously.But in the Liao Dynastyization, the adding of the trisodium phosphate aqueous solution makes the fouling of oxidation preheater, and needing regularly stops cleans, and has influenced the continuous production cycle of device; And the technology of the misery ester that phosphorates, effect is not remarkable.The shortcoming of a maximum of hexanaphthene non-catalyst oxidation method is that the inductive phase of oxidizing reaction is very long, when oxidizing reaction begins, owing to do not have transition-metal catalyst in the oxidation reactor material, there is not radical yet, therefore the speed of initiation reaction is very slow, conventional device all will be made into the oxygen-deficient mixture body with air and nitrogen, begin to feed a small amount of this oxygen-deficient mixture body from first oxidation reactor lentamente, initiation reaction, radical concentration is slowly raise, thereby speed of response progressively improves, in order to accelerate this process, patent report was once arranged, when oxidizing reaction begins, the pimelinketone of the easy oxidation of adding and hexalin etc. in hexanaphthene, and to make its content be 0.1～3%, facts have proved, the initiating method of this adding pimelinketone and hexalin, and not really produce effect, because though pimelinketone and hexalin are than the easy oxidation of hexanaphthene, but also belong to the free radical reaction process, after needing the pimelinketone hexalin oxidation of some amount, could in material, accumulate certain density radical, just can make cyclohexane oxidation speed reach normal level in several hours later on, therefore present non-catalyst oxidation method technology, it is normal that the driving time all wants more than several hrs even 10 just to reach oxidizing reaction in individual hour.
The purpose of this invention is to provide a kind of modification method for preparing pimelinketone and hexalin from cyclohexane oxidation, when cyclohexane oxidation begins, add transition-metal catalyst, make that oxidizing reaction speed is very fast to reach normal level, guarantee the safety when cyclohexane oxidation begins, guarantee that promptly the oxidized tail gas oxygen level reaches about 2% very soon, can make cyclohexane oxidation forward the non-catalyst oxidation method to then again very soon, and reach the optimized condition of hexanaphthene non-catalyst oxidation, the yield of cyclohexane oxidation is obviously improved.
The objective of the invention is to be achieved through the following technical solutions:
(1), under pressure 0.8～2.0Mpa condition,, generates the oxidation liquid mixture that contains pimelinketone, hexalin and cyclohexyl hydroperoxide with the gas cyaniding hexanaphthene of molecule-containing keto 140～200 ℃ of temperature;
(2) 50～170 ℃ of temperature, under pressure 0.001～2.0Mpa condition, carry out homogeneous catalysis with the oil soluble transition-metal catalyst and decompose, perhaps in alkaline aqueous solution, carry out heterogeneous catalysis and decompose, cyclohexyl hydroperoxide is decomposed generate pimelinketone and hexalin with transition-metal catalyst;
(3) with rectifying tower separating benzene-cyclohexane, pimelinketone and hexalin;
The method is characterized in that, when cyclohexane oxidation began, the soluble transition metal salt that adds 0.1～100ppm in hexanaphthene was made catalyzer, the initiated oxidation reaction, the diphosphonate ester that adds 0.1～10ppm is simultaneously made precipitating inhibitor, adopts the catalytic oxidation technology of hexanaphthene to produce; After cyclohexane oxidation is normal, stop immediately in the hexanaphthene of oxidation reactor, adding transition metal salt catalyst, but keep the diphosphonate ester that in the hexanaphthene of oxidation reactor, adds 0.05～1ppm always, make reactor metal wall and material and carry the passivator of trace metal ion secretly, prevent the decomposition of cyclohexyl hydroperoxide in oxidation reactor, adopt hexanaphthene non-catalyst oxidation method technology to produce.When cyclohexane oxidation began, the soluble transition metal salt catalyst that joins in the hexanaphthene was cobalt naphthenate or cobalt octoate, Cobalt Porphyrin, and chromium naphthenate, chromic acid tert-butyl, preferably adding concentration is that the concentration of transition metal in hexanaphthene is 0.1～3ppm.The adding of these transition-metal catalysts, accelerated the oxidizing reaction speed when cyclohexane oxidation begins greatly, make in the several minutes of cyclohexane oxidation after beginning just to have reached normal oxygen absorption rate, promptly oxygen content reaches normal controlling index about 2% very soon in the oxidized tail gas.When cyclohexane oxidation begins, adding diphosphonate ester simultaneously is very important, the mol ratio that the add-on of diphosphonate ester is controlled at diphosphonate ester and transition metal is 1: 5～10, such add-on can not influence the catalytic activity of transition metal salt, can guarantee that again transition-metal catalyst can not cause the slagging scorification precipitation, guaranteed the cleaning of cyclohexane oxidation device, for cyclohexane oxidation speed normal after, carry out the transition to the non-catalyst oxidation method more very soon and created condition.The chemical general formula that adds the diphosphonate ester in the hexanaphthene in the oxidation system is:
In the formula, m1=0,1 or 2, n1=2-m1; M2=0,1 or 2, n2=2-m1; M1 and m2 are not 0 or 2 simultaneously; R is the alkyl of H or 1～18 carbon atom; R ', R " can be identical, also can be inequality; R ', R " be the alkyl of 4～18 carbon atoms; X is H or OH.Preferred diphosphonate ester is a 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid (two) 2-(ethyl hexyl) ester, and chemical formula is
Preferred add-on is that the concentration of diphosphonate ester in hexanaphthene is 0.3～0.5ppm.No matter be hexanaphthene catalytic oxidation or hexanaphthene non-catalyst oxidation method, also no matter which kind of initiation mode is the non-catalyst oxidation method adopt when beginning, it all is necessary adding a certain amount of diphosphonate ester; When implementing hexanaphthene catalytic oxidation industrial production, add diphosphonate ester and can avoid the slagging scorification of hexanaphthene catalytic oxidation technology to stop up, guarantee the long period safety in production of hexanaphthene catalytic oxidation; When implementing hexanaphthene non-catalyst oxidation method industrial production, add diphosphonate ester, the trace metal ion of carrying secretly in metal wall that can the passive oxidation reactor and the material, reduce the decomposition of cyclohexyl hydroperoxide in oxidation reactor, thereby significantly improve the oxidization-hydrogenation ratio of hexanaphthene non-catalyst oxidation method.Need to prove that hexanaphthene non-catalyst oxidation method is when the reaction beginning, no matter with which kind of initiation mode, for example add transition-metal catalyst and cause, perhaps add pimelinketone, hexalin, acetaldehyde causes, perhaps Poor oxygen gas circulation bubbling causes under the high temperature, in case oxidizing reaction speed is normal, enters into hexanaphthene non-catalyst oxidation method nominal situation, all need continuously to add in the hexanaphthene in oxidation reactor the diphosphonate ester of trace, so that significantly improve the yield of hexanaphthene non-catalyst oxidation method.Give more detailed explanation below in conjunction with embodiment to the present invention.
Embodiment 1:
In 5 liters of batch oxidation reactor of reflux exchanger are housed, 3.5 liters of content are housed greater than 99.9% pure hexanaphthene, and in hexanaphthene, add the cobalt octoate of 1ppm and the diphosphonate ester of 1ppm, with nitrogen pressure is raised to 1.1Mpa, temperature is raised to 165 ℃ with electric heating piece, evenly feeding altogether in 30 minutes, 120 litres of air bubblings carry out oxidation, oxidized tail gas is through behind the condenser, emptying under 1.1Mpa pressure, oxygen content is 2% by analysis in the emptying tail gas, Returning reactor after the hexanaphthene condensation of gas in the tail gas.Reaction finishes the back decrease temperature and pressure, emit the cyclohexane oxidation mixed solution, carry out chemical analysis, contain cyclohexyl hydroperoxide 0.5% (mole) in this oxidation mixture, pimelinketone 0.8% (mole), hexalin 1.9% (mole), acid 0.32% (mole), ester 0.24% (mole), all the other are hexanaphthene, conversion rate of oxidation 3.6% (mole).This embodiment proves cobalt metal-salt catalysis cyclohexane oxidation well, and inductive phase in when beginning reaction is not obvious, and hexanaphthene just reaches the normal oxidation speed of response very soon behind the bubbling air.
Comparative Examples A:
Device, hexanaphthene add-on, blowing air amount, reaction times, temperature of reaction and reaction pressure are all identical with embodiment 1, just do not add transition metal salt catalyst and diphosphonate ester, the emptying behind condenser under 1.1Mpa too of oxidizing reaction tail gas; Analyze oxidized tail gas, the oxygen level in the tail gas is on average 14%, and during near reaction end, the tail gas oxygen level just drops to 8%.The cyclohexane oxidation mixed solution of getting in the oxidation reactor is analyzed, this oxidation mixture contains cyclohexyl hydroperoxide 0.4% (mole), pimelinketone 0.1% (mole), hexalin 0.2% (mole), other oxide compound 0.1% (mole) such as acid esters, all the other 99.2% (moles) are hexanaphthene, and conversion rate of oxidation is 0.8% (mole).This comparative example proves hexanaphthene under the situation of no transition-metal catalyst and other initiator, during the reaction beginning inductive phase very long, behind the bubbling air, hexanaphthene can not reach the normal oxidation speed of response very soon.
Comparative example B:
Device, hexanaphthene add-on, blowing air amount, reaction times, temperature of reaction and reaction pressure are all identical with embodiment 1, just do not add transition metal salt catalyst and diphosphonate ester, but in hexanaphthene, add 0.3% mole of pimelinketone, hexalin and cyclohexyl hydroperoxide; Oxidizing reaction tail gas is analyzed oxidized tail gas too in 1.1Mpa emptying behind condenser, and the oxygen level in the tail gas is on average 6%, and tail gas contains the oxygen height during reaction beginning, to 12%, surpasses safety index, and during near reaction end, oxygen level just drops to 3% in the tail gas.The cyclohexane oxidation mixed solution of getting in the oxidation reactor is analyzed, this oxidation mixture contains cyclohexyl hydroperoxide 2.0% (mole), pimelinketone 0.3% (mole), hexalin 0.5% (mole), other oxide compound 0.3% (mole) such as acid esters, all the other 96.9% (moles) are hexanaphthene, and conversion rate of oxidation is 3.1% (mole).This comparative example illustrates that cyclohexyl hydroperoxide, pimelinketone, hexalin can accelerate the speed of response of cyclohexane oxidation, but effect does not have transition metal salt catalyst obvious.
Embodiment 2
In the 1st reactor of a series of placed in-line 5 reactors (50 liters of each volumes), add 160 kilograms/hexanaphthene hourly continuously, these hexanaphthenes pass through the 2nd, 3,4,5 reactors according to the order overflow, in the hexanaphthene that enters first reactor, add cobalt naphthenate, make that to contain the cobalt amount in the hexanaphthene be 1ppm, and add the 1ppm diphosphonate ester simultaneously.Suppress 1.0Mpa with nitrogen, hexanaphthene is preheating to 165 ℃ by preheater and adds first reactor, logical pressurized air carries out oxidation under this pressure and temperature, tail gas is emptying behind condenser, hexanaphthene in the tail gas returns the 1st reactor after condensation, air feeding amount reaches 1000 liters after 2 hours, and reaction is normal, oxygen level is 2% in the oxidized tail gas, and cyclohexane conversion is 3% (mole); Improve reaction pressure to 1.15Mpa, stop to add the cobalt naphthenate catalyzer in hexanaphthene, but keep the diphosphonate ester that adds 0.4ppm in hexanaphthene, the hexanaphthene catalytic oxidation has just carried out the transition to the normal hexanaphthene non-catalyst oxidation of operating mode method reposefully.This embodiment proves that after cyclohexane oxidation began, oxidizing reaction speed reached normally very soon, drives steadily, and safety, rapidly; The adding of diphosphonate ester, make it in the not slagging scorification of stage of hexanaphthene catalytic oxidation, especially in the hexanaphthene non-catalyst oxidation method stage, the diphosphonate ester passivation trace metal ion carried secretly of oxidation reactor metal wall and material, reduced the decomposition of cyclohexyl hydroperoxide, make very transparent clear of cyclohexane oxidation mixed solution, obtained the best oxidization-hydrogenation ratio of hexanaphthene non-catalyst oxidation method.After the cyclohexane oxidation mixture passed through cyclohexyl hydroperoxide decomposition process rectification working process again, the yield that hexanaphthene prepares pimelinketone, hexalin was 82%.
The comparative example: with embodiment 2 identical conditions under, only change when cyclohexane oxidation begins, do not add transition-metal catalyst, (if 1.0Mpa, 165 ℃ feed pressurized air down, and security incident may appear in not oxidation.) pressure is brought up to 1.15Mpa, under 168 ℃, feed 100 liters of Poor oxygen gas that contain oxygen 10% to the 1st reactor, (blowing air is dangerous), after half an hour, oxygen level drops to 3% in the tail gas, could feed 20 air that contract that boost to the 2nd reactor after 1 hour, could feed pressurized air to the 3rd reactor after 2 hours, could feed pressurized air to the 4th reactor after the 3rd hour, could feed pressurized air to the 5th reactor after 4 hours; Enter hexanaphthene non-catalyst oxidation nominal situation, 5 to 14 hours.Under successive hexanaphthene non-catalyst oxidation method operating mode, produce the cyclohexane oxidation mixture, pass through cyclohexyl hydroperoxide decomposition process and rectification working process again, because do not implement to add the technology of diphosphonate ester, the total recovery that hexanaphthene prepares pimelinketone, hexalin is 80%.
Embodiment 3:
In the 1st reactor of a series of placed in-line 5 reactors (50 liters of each volumes), add 160 kilograms/hexanaphthene hourly continuously, these hexanaphthenes pass through the 2nd according to the order overflow, 3,4,5, reactor, in the hexanaphthene that enters first reactor, add Cobalt Porphyrin 8pmm, suppress 0.8Mpa with nitrogen, hexanaphthene is preheating to 145 ℃, logical pressurized air carries out oxidation under this pressure and temperature, tail gas is emptying after condensation, return the 1st reactor after the hexanaphthene condensation in the tail gas, air feeding amount reaches 1500 liters after 2 hours, reaction is normal, and oxygen level is 2% in the oxidized tail gas, and cyclohexane conversion is 4.5% (mole); Continuous production is 5 days under this operating mode, finds that oxidation reactor and associated pipe have the slagging scorification latch up phenomenon, and the cyclohexane oxidation mixture decomposes and rectification working process through cyclohexyl hydroperoxide, and the total recovery that hexanaphthene prepares pimelinketone, hexalin is 70%.Buck and artificial the cleaning are carried out in parking, after cleaning end, hexanaphthene non-catalyst oxidation law part according to the comparative example of embodiment 2 is driven, but oxygen level descends in the tail gas, cyclohexyl hydroperoxide content in the cyclohexane oxidation mixture descends, pimelinketone, oxygenates level such as hexalin and acid esters rises, continuous production is one month under this operating mode, hexanaphthene prepares pimelinketone, the total recovery of hexalin is 76%, reason is the pollution that material and reactor pipeline all have been subjected to the transition-metal catalyst Cobalt Porphyrin, in order to address this problem, in the hexanaphthene of the 1st reactor is reinforced, add the diphosphonate ester of 1ppm continuously, find after 1 hour that cyclohexyl hydroperoxide content in the cyclohexane oxidation mixture rises to the normal value of non-catalyst oxidation method, continuous production under this operating mode, hexanaphthene prepares pimelinketone, the total recovery of hexalin is 82%, has reached hexanaphthene non-catalyst oxidation method yield preferably.
Embodiment 4:
In the 1st reactor of a series of 5 reactors (50 liters of each volumes), add 160 kilograms/hexanaphthene hourly continuously, these hexanaphthenes pass through the 2nd according to the order overflow, 3,4,5 reactors, suppress 1.2Mpa with nitrogen, the ON cycle compressor, make nitrogen pass through reactor, tail gas condenser circulates, internal circulating load is 500 liters/hour, when hexanaphthene being raised to 140 ℃ with preheater, add to each reactor respectively and contain 3 liters of trisodium phosphate 2% aqueous solution, carry out trisodium phosphate and be coated with wall, passivation reaction device metal wall, condensation hexanaphthene in the recycled offgas returns the 1st reactor, water is discharged system, after being coated with wall and finishing, with the nitrogen pressurize to 1.9Mpa, hexanaphthene is preheating to 190 ℃, in cyclohexane feed, add the 0.1ppm trisodium phosphate continuously and be coated with wall (adding) with the aqueous solution to keep burnt sodium, slowly to recycle compressor import bubbling air, make per 5 minutes of the gas that enters oxidation reactor increase oxygen level 0.25%, be increased to into the oxygen content gas of oxidation reactor always and be till 14%; Carry out the tail gas emptying simultaneously, make the tail gas oxygen level remain on 2%, the enforcement trisodium phosphate is coated with the High Temperature High Pressure oxygen deprivation hexanaphthene non-catalyst oxidation method under the wall condition.The cyclohexane oxidation mixture decomposes and rectification working process through cyclohexyl hydroperoxide, and the total recovery that cyclohexane oxidation prepares pimelinketone, hexalin is 82%.In this embodiment, the cancellation trisodium phosphate is coated with wall and adds continuously, change the diphosphonate ester that in cyclohexane feed, adds 0.1ppm continuously into, so just simplified operation, solved and added the difficult problem that the hexanaphthene preheater is stopped up in the trisodium phosphate slagging scorification, and the yield that makes cyclohexane oxidation prepare pimelinketone, hexalin brings up to 83%
Claims (6)
1. one kind prepares the method for pimelinketone and hexalin from cyclohexane oxidation, and this method comprises the following steps:
(1) under 140～200 ℃ of temperature, pressure 0.8～2.0Mpa condition,, generates the oxidation liquid mixture that contains pimelinketone, hexalin and cyclohexyl hydroperoxide with the gas cyaniding hexanaphthene of molecule-containing keto;
(2) under 50～170 ℃ of temperature, pressure 0.001～2.0Mpa condition, carry out the homogeneous catalysis decomposition or in alkaline aqueous solution, carry out heterogeneous decomposition with the oil soluble transition-metal catalyst, cyclohexyl hydroperoxide is decomposed generate pimelinketone and hexalin with transition-metal catalyst;
(3) use the rectifying tower separating benzene-cyclohexane, pimelinketone and hexalin;
The method is characterized in that, when cyclohexane oxidation begins, the soluble transition metal salt that adds 0.1～100ppm in hexanaphthene is done catalyzer initiated oxidation reaction, and the diphosphonate ester that adds 0.1～10ppm is simultaneously made precipitating inhibitor, adopts the catalytic oxidation technology of hexanaphthene to produce; After cyclohexane oxidation is normal, stop in the hexanaphthene of oxidation reactor, adding transition metal salt catalyst, but keep the diphosphonate ester that in the hexanaphthene of oxidation reactor, adds 0.05～1ppm always, make reactor metal wall and material and carry the passivator of trace metal ion secretly, prevent that cyclohexyl hydroperoxide from decomposing in oxidation reactor, adopt hexanaphthene non-catalyst oxidation method technology to produce.
2. according to the method for claim 1, the soluble transition metal salt catalyst that it is characterized in that adding the initiated oxidation reaction in the hexanaphthene is cobalt naphthenate, cobalt octoate, Cobalt Porphyrin or chromium naphthenate, chromic acid tert-butyl.
3. according to the method for claim 1, when it is characterized in that oxidizing reaction begins, the concentration that adds the initiated oxidation catalyst for reaction in the hexanaphthene is 0.1～3ppm.
4. according to the method for claim 1, the chemical general formula that it is characterized in that adding the diphosphonate ester in the hexanaphthene in the oxidation system is:
In the formula, m
1=0,1 or 2; n
1=2-m
1m
2=0,1 or 2; n
2=2-m
2m
1And m
2Be not 0 simultaneously or be 2; R is the alkyl of H or 1～18 carbon atom; R ', R " can be identical, also can be inequality; R ', R " be the alkyl of 4～18 carbon atoms; X is H or OH.
5. according to the method for claim 1, it is characterized in that adding that the diphosphonate ester in the hexanaphthene is 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid (two) 2-(ethyl hexyl) ester in the oxidation system, chemical formula is
6. according to the method for claim 1, it is characterized in that the concentration of the diphosphonate ester in the hexanaphthene during adding oxidizing reaction is is 0.3～0.5ppm.
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| CN101085714B (en) * | 2006-06-06 | 2011-12-07 | 中国石油化工集团公司 | Method for preparing cyclohexanone and cyclohexanol by oxidizing cyclohexane |
| CN102012188B (en) * | 2010-10-28 | 2012-11-28 | 中国石油化工股份有限公司 | Anti-corrosion method for tail gas heat exchange tower in cyclohexane oxidation technology |
| CN102179265B (en) * | 2011-03-16 | 2013-04-10 | 中国科学院长春应用化学研究所 | Catalyst for use in preparation of cyclohexanol and cyclohexanone and method for preparing cyclohexanol and cyclohexanone |
| CN102627541B (en) | 2012-03-28 | 2014-07-23 | 湖北三宁化工股份有限公司 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
| CN102627542B (en) * | 2012-03-28 | 2014-05-21 | 肖藻生 | Process for preparing hexanaphthene and cyclohexanone with cyclohexane serving as raw material |
| CN102627525B (en) * | 2012-03-31 | 2013-12-25 | 肖藻生 | Preparation process for preparing hexamethylene and cyclohexanone by cyclohexane oxidation |
| CN107400038B (en) * | 2016-05-20 | 2020-08-21 | 中国石油化工股份有限公司 | Method for preparing cyclohexanone and cyclohexanol by decomposing cyclohexyl hydroperoxide |
| CN106348997B (en) * | 2016-08-25 | 2019-09-24 | 湖北三宁化工股份有限公司 | The method and device of transition metal in a kind of removal hexamethylene |
| CN109020858B (en) * | 2018-09-11 | 2021-03-05 | 中国海洋石油集团有限公司 | Method for inhibiting decomposition of ethylbenzene hydroperoxide |
| CN112439452B (en) * | 2019-09-04 | 2023-07-04 | 中国石油化工股份有限公司 | Catalyst for preparing adipic acid by direct oxidation of cyclohexane |
| CN113509888B (en) * | 2020-04-10 | 2022-11-22 | 中国石油化工股份有限公司 | Gas feed system |
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| CN1035960A (en) * | 1988-09-16 | 1989-10-04 | 肖藻生 | A kind of complex catalyst of hydrocarbon oxidation |
| CN1253938A (en) * | 1998-11-12 | 2000-05-24 | 肖藻生 | Method for preparing cyclohexanol and cyclohexanone |
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| CN1035960A (en) * | 1988-09-16 | 1989-10-04 | 肖藻生 | A kind of complex catalyst of hydrocarbon oxidation |
| CN1253938A (en) * | 1998-11-12 | 2000-05-24 | 肖藻生 | Method for preparing cyclohexanol and cyclohexanone |
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