CN1105970A - process for preparing cyclohexanol and cyclohexanone from cyclohexane - Google Patents
process for preparing cyclohexanol and cyclohexanone from cyclohexane Download PDFInfo
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- CN1105970A CN1105970A CN 94110939 CN94110939A CN1105970A CN 1105970 A CN1105970 A CN 1105970A CN 94110939 CN94110939 CN 94110939 CN 94110939 A CN94110939 A CN 94110939A CN 1105970 A CN1105970 A CN 1105970A
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- cyclohexanone
- cyclohexane
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 86
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- 230000003647 oxidation Effects 0.000 claims abstract description 44
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 40
- 238000005516 engineering process Methods 0.000 claims description 19
- -1 transition metal salt Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 8
- 238000007172 homogeneous catalysis Methods 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229930194542 Keto Natural products 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 238000007127 saponification reaction Methods 0.000 description 13
- 239000003513 alkali Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- 240000005373 Panax quinquefolius Species 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 208000018459 dissociative disease Diseases 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000007791 liquid phase Substances 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
- 101710171243 Peroxidase 10 Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005340 bisphosphate group Chemical group 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
The invention discloses a process for preparing cyclohexanol and cyclohexanone from cyclohexane, which comprises oxidizing cyclohexane with gas containing molecular oxygen in an oxidation reactor to generate an oxidation mixture containing cyclohexyl perhydrogen, (8) decomposing the oxidation mixture to generate cyclohexanol and cyclohexanone, and (C) separating in a separator to distill out cyclohexanone and cyclohexanol products. It is characterized in that the process for decomposing the oxidation mixture containing cyclohexyl hydroperoxide is carried out in two steps. The first step is carried out under neutral or acidic conditions and the second step is carried out under strongly basic conditions.
The invention greatly improves the molecular yield of cyclohexanone and cyclohexanol, reduces consumption and reduces cost.
Description
The present invention relates to from the cyclohexane preparation ring technology of alcohol, cyclohexanone.
Encircle the preparation of alcohol, cyclohexanone at present, normally use the gas cyaniding cyclohexane of molecule-containing keto, generate the oxidation mixture that contains the cyclohexyl hydrogen peroxide, handle this oxidation mixture then and make cyclohexyl hydrogen peroxide decomposition production ring pure, cyclohexanone.Two kinds of technology approach are generally arranged, a kind of is that homogeneous catalysis is decomposed, a kind of is that heterogeneous catalysis is decomposed, and these two kinds of technologies all are that one step of processing of oxidation mixture is finished, and the transformation efficiency of its cyclohexyl hydrogen peroxide dissociation reaction or generation ring molecular yield pure, cyclohexanone is undesirable.
The purpose of this invention is to provide and a kind ofly prepare cyclohexanone and the ring technology of alcohol from cyclohexane, make the transformation efficiency of cyclohexyl hydrogen peroxide dissociation reaction and generate ring the molecular yield of alcohol, cyclohexanone greatly improve, and reduce and consume, reduce cost.
The object of the present invention is achieved like this.
The present invention includes: the oxidation mixture that (A) in oxidation reactor, contains the cyclohexyl hydrogen peroxide with the gas cyaniding cyclohexane production of molecule-containing keto; (B) oxidation mixture that will contain the cyclohexyl hydrogen peroxide decomposes, and produces cyclohexanol and cyclohexanone; (C) in separator, distill out cyclohexanone and ring alcohol after the separation.
The technology that it is characterized in that decomposing the oxidation mixture that contains the cyclohexyl hydrogen peroxide divided for two steps carried out.
The first step is decomposed with heterogeneous catalysis technology in the PH=5-8 scope or is decomposed with homogeneous catalysis technology under acidic conditions.
Second step is at PH〉decompose with the heterogeneous catalysis decomposition technique under 13 the strong alkaline condition.And need not carry out separating treatment after the first step decomposition reaction, set about carrying out second step immediately and decompose.
It is at 80-155 ℃ that described heterogeneous catalysis is decomposed, and pressure 100KPa-1200KPa is that the water-soluble transition metal salt of 0.3-1000ppm is made catalyzer with concentration, handles oxide compound in the presence of the alkali metal hydroxide and the organic acid salt aqueous solution.
It is 80 °-155 ℃ of temperature that described homogeneous catalysis is decomposed, and under the pressure 100KPa-1200KPa condition, is that the oil soluble transition metal salt of 0.3-1000ppm is made the catalyst treatment oxidation mixture with concentration.
Described transition metal salt with catalyzer is cobalt salt or chromic salts.
Below in conjunction with embodiment the present invention is described in detail:
The embodiment of the invention 1:
The technical process of present embodiment as shown in Figure 1.
In oxidation reactor, add the 160000kg/h cyclohexane, 165 ℃ of controlled temperature, pressure 1200KPa does not add catalyzer, make cyclohexane in liquid phase by molecular oxygen partial oxidation in the air, the transformation efficiency of cyclohexane is about 4.5mol%.Per hour contain the about 15400kg of cyclohexane, ring pure 1275kg, pimelinketone 538kg, cyclohexyl hydrogen peroxide 5475kg in the oxidation mixture of Sheng Chenging, and other by product.This oxidation mixture is after heat exchange and cooling, and temperature is about 70 ℃, enters first decomposition reactor, adds the heterogeneous catalyst Cobaltous diacetate aqueous solution, makes Co in the decomposition reactor
++Content is 1ppm, add 3%NaOH circulation alkali 2000kg/h, make the PH of No. 1 splitter be controlled at 7 ± 1, temperature is controlled at about 95 ℃, pressure-controlling is about 1200KPa, decomposition reaction in this reactor is owing to be to decompose under neutrallty condition, the reaction conditions gentleness, and the cyclohexyl hydrogen oxide decomposes the molecular yield of producing cyclohexanol and cyclohexanone and improves.Send into decomposition reactor again No. 2.In No. 2 decomposition reactors, add 13%NaOH fresh soda 5100kg/h by pipeline 7, control PH〉13, about 95 ℃ of temperature, pressure 1200KPa proceeds to decompose.Because strong basicity has been accelerated decomposition reaction velocity, makes the cyclohexyl hydrogen peroxide decomposition complete.Per hour contain cyclohexane 153800kg in the degradation production, hexalin 3065kg, pimelinketone 3294kg.In this two steps decomposition technique, the molecular yield that the cyclohexyl hydrogen peroxide decomposition generates cyclohexanol and cyclohexanone is 92%.Degradation production upper oil phase after standing demix separates is sent to quiet cut from, cyclohexane Returning oxidation reactor wherein.Per hour get cyclohexanol and cyclohexanone 6359kg.Lower floor's buck part mutually is circulated to decomposition reactor No. 1, and remaining sends to the salkali waste treatment unit.
The comparative example 1:
Identical with Fig. 1 implementing process flow process.
The oxidation reactor condition is identical, and oxidation mixture contains cyclohexane, and hexalin, cyclohexanone amount are identical, enter first decomposition reactor after, it is identical to add heterogeneous catalyst Cobaltous diacetate amount.Add 5600 kilograms/hour of 3% NaOH circulation alkali 34000kg/h and 13% NaOH fresh sodas at first decomposition reactor, make the PH of first reactor〉13, about 85 ℃ of controlled temperature, pressure 1200KPa, because this decomposition reaction is carried out under strong alkaline condition, decomposition rate is fast, the molecular yield that decomposes the cyclohexanol and cyclohexanone that generates is lower, carry out decomposition reactor again No. 2, No. 3, with No. 1 decomposition reactor the same terms under decompose again, the cyclohexyl hydrogen peroxide is decomposed fully.At this moment, the molecular yield of cyclohexanol and cyclohexanone is 88%.Per hour contain cyclohexane 153900kg in the degradation production, encircle pure 2914kg, cyclohexanone 3186kg.Degradation production separates through standing demix, and upper oil phase is sent rectifying separation, per hour gets cyclohexanone, the pure 6100kg of ring, and cyclohexane is Returning oxidation reactor then.
The embodiment of the invention 2
The present embodiment technical process as shown in Figure 2.
Be respectively 10m at four volumes
3Oxidation reactor in, per hour add the 30000kg cyclohexane continuously, contain CATALYST Co in the retaining ring hexane
++0.3ppm, under 156 ℃ and 1000KPa, with molecular oxygen partial oxidation cyclohexane in the air.Per hour must contain cyclohexane 28400kg, encircle pure 700kg, cyclohexanone 370kg, cyclohexyl hydrogen peroxide 520kg, adipic acid 180kg, ester 140kg, and the oxidation mixture of a small amount of other by products.This oxidation mixture is overflowed in the splitter, at 1000KPa, proceed thermolysis and homogeneous catalysis under 130 ℃ and decompose, cyclohexyl superoxide rates of decomposing and transforming in this splitter is 20%, enters saponification column.Add 3%NaOH circulation alkali 4000kg in the saponification column bottom, make saponification column lower semisection PH=7 ± 1, controlled temperature be 130 ℃, pressure 1200KPa, since the pH value of saponification column lower semisection than splitter height, the adding of a large amount of circulation alkali and emulsification takes place, decomposition reaction velocity is accelerated, and most of cyclohexyl hydrogen peroxide decomposes under neutral emulsification condition, adds the 1500kg13%NaOH fresh soda in addition in pipeline 3, make saponification column upper semisection basicity rise PH〉13.Saponification column ejects a mouthful aqueous phase and contains more than the NaOH3%, and decomposition reaction velocity is accelerated, and the cyclohexyl hydrogen peroxide is decomposed fully.And the material that makes saponification column upper semisection and back is reemulsification not, and the layering that is beneficial to the back separator separates.In separator, upper oil phase is sent to rectifying separation, isolated cyclohexane Returning oxidation reactor.Per hour get cyclohexanol and cyclohexanone 1540kg.Lower floor's buck contains NaOH3% mutually, water 50-60%, and organic acid sodium salt 37-47% per hour is circulated to saponification column bottom 4000kg, and remaining sends to the salkali waste treatment unit.The molecule rate of recovery of cyclohexyl hydrogen peroxide decomposition generation cyclohexanol and cyclohexanone is 90% in this technology.In this technology, also can add circulation alkali and carry out the neutral decomposition of the first step at splitter, add fresh soda at saponification column and carry out the strong basicity decomposition of second step, also can in splitter, add outside the soluble transition metal of higher concentration, strengthen the homogeneous decomposition of the first step.
The comparative example 2
Technical process and oxidation reactor condition and embodiment 2 are identical, gained oxidation mixture amount is also identical, condition is identical in the splitter, after entering saponification column, per hour add 13%NaOH fresh soda 1800kg from No. 1 pipeline, No. 2 pipeline adds 3%NaOH circulation alkali 3000kg again, this moment PH 130 ℃ of 13 controlled temperature, pressure 1200KPa, rectifying got cyclohexanol and cyclohexanone 1410kg/ hour after material separated in separator after decomposing.The molecular yield of cyclohexyl hydrogen peroxide decomposition generation cyclohexanol and cyclohexanone is 64% in this technology.
The embodiment of the invention 3
The present embodiment technical process as shown in Figure 3.
This routine oxidation reactor and decomposition reactor are a still four Room or a still five Room.Per hour by molecular oxygen oxidation in the air, the controlled oxidation temperature of reaction is 156 ℃ to the 160000kg cyclohexane in liquid phase, and pressure 1000KPa adds cobalt octoate and makes homogeneous oxidation catalyst, control CO
++Concentration is 1ppm, and a small amount of long-pending bisphosphate of adding prevents slagging scorification.Per hour air feeding amount is 8700MM
3, per hour contain cyclohexane 152800kg in the oxidation mixture of Sheng Chenging, encircle pure 3329kg, cyclohexanone 1056kg, cyclohexyl hydrogen peroxide 1440kg, adipic acid 582kg, ester 515kg, other by products 674kg.During above oxidation mixture is sent to and decomposition reactor A chamber at pressure 1000KPa, under 150 ℃ of conditions of temperature, was sent 3% NaOH circulation alkali into the A chamber of decomposition reactor in 20000kg/ hour, made A chamber PH=7 ± 1, emulsification takes place decompose.Then material is overflowed to the B chamber again, per hour add 13%NaOH fresh soda 5400kg from pipeline 3 to the B chamber, make B chamber PH 13.Material enters separator, and there is anti-phase rectifying separation on the upper strata, isolating cyclohexane Returning oxidation reactor.Per hour get cyclohexanol and cyclohexanone product 6279kg, the molecular yield that its cyclohexyl hydrogen peroxide decomposition generates cyclohexanol and cyclohexanone is 90%.Lower floor's water contains 3% NaOH and 27-47% has antiacid sodium salt, is partly recirculated to decomposition reactor A chamber.Remaining enters salkali waste and handles.
The comparative example 3.
Technical process as shown in Figure 3.
The condition of oxidation reactor and embodiment 3 are identical, oxidation mixture is sent into decomposition reactor A chamber, under pressure 1000KPa, 150 ℃ of conditions of temperature, per hour add 13%NaOH fresh soda 6400kg from pipeline 1, add 3%NaOH circulation alkali 2000kg from pipeline 2 to the A chamber, in carrying out and decomposition reaction.And then overflow enters B chamber and C chamber, and further neutralization enters separator after decomposing.Upper oil phase is sent to rectifying separation, per hour must encircle alcohol, cyclohexanone product 6040kg, and the molecular yield that its cyclohexyl hydrogen peroxide decomposition generates cyclohexanol and cyclohexanone is 54%.
The embodiment of the invention 4.
Technical process as shown in Figure 4.
At 4 32m
2Vertical oxidizing reaction tower in, per hour send into 140000 kilograms of cyclohexanes, control 1,2,3, the temperature of No. 4 oxidizing reaction towers is 181 ℃, 176 ℃, 170 ℃, 166 ℃, pressure 1900KPa, do not add catalyzer, from the 4th oxidizer, discharge oxidation mixture, through give concentrate and dehydration after, enter decomposition reactor, at pressure 300KPa, 92 ℃ of temperature and 6ppm chromic acid tert-butyl catalyzer exist down, stop 30 minutes, cyclohexyl hydrogen peroxide generation homogeneous catalysis is decomposed, decompose the after product composition and be approximately cyclohexane 91.5%, cyclohexyl hydrogen peroxidase 10 .5%, ring is alcohol, cyclohexanone 7.2%, other components 0.8%, above material is sent into neutralization decompose the saponification reaction device, per hour add and close 13%NaOH fresh soda 2000kg, add 3%NaOH circulation alkali 10000kg from pipeline 2 from pipeline 1, make in the material acid obtain neutralization, ester obtains saponification.Heterogeneous catalysis further takes place and decomposes in remaining cyclohexyl hydrogen peroxide (PH〉13) under strong alkaline condition.Reaction mass is through standing demix, separation.Lower floor is a water, contains 3% NaOH and some organic acid sodium salts, per hour has 1000kg to be circulated to decomposition, saponification reaction device, and remaining enters salkali waste and handles.The oil phase rectifying tower of making a gift to someone, the cyclohexane Returning oxidation reactor that steams per hour must contain ring each 5600kg of product of alcohol, cyclohexanone 99.0%.
The comparative example 4
Technical process, condition are identical with embodiment 4.Difference is that the product after homogeneous catalysis is decomposed is directly sent into rectifying tower and separated.The cyclohexane Returning oxidation reactor that steams per hour must contain ring alcohol, the alcohol of cyclohexanone 98.0%, each 5360kg of ketone product.
The present invention prepares cyclohexanone, the ring technology of alcohol by cyclohexane, and ring molecular yield pure, cyclohexanone is greatly improved, and has reduced consumption, has reduced cost.
Claims (4)
1, a kind of from cyclohexane prepare cyclohexanone and the ring alcohol technology.May further comprise the steps:
A, in oxidation reactor, 140 °-180 ° of controlled temperature under the pressure 900-1200KPa condition, generate the oxidation mixture that contains the cyclohexyl hydrogen peroxide with the gas cyaniding cyclohexane of molecule-containing keto;
B, the oxidation mixture that will contain the cyclohexyl hydrogen peroxide decompose, and make the generation cyclohexanol and cyclohexanone;
C, in separator, separate after, oil phase enters distiller, distills out cyclohexanone and the pure product of ring.Isolating cyclohexane Returning oxidation reactor;
It is characterized in that, decompose the technology of the oxidation mixture that contains the cyclohexyl hydrogen peroxide and divided for two steps carried out:
The first step is decomposed with heterogeneous catalysis technology in the PH=5-8 scope or is decomposed with homogeneous catalysis technology under acidic conditions.
Second step was decomposed further decomposition with the heterogeneous catalysis decomposition technique under the strong alkaline condition of PH＞13.And the second step decomposition reaction is not need to carry out separating treatment after the first step decomposition reaction immediately.
2, prepare cyclohexanone and the pure technology of ring according to claim 1 is described from cyclohexane, it is characterized in that, it is at 80 °-155 ° that described heterogeneous catalysis is decomposed, pressure 100KPa-1200KPa, water-soluble transition metal salt with concentration 0.3-1000ppm is made catalyzer, handles oxide compound in the presence of the alkalimetal oxide and the organic acid salt aqueous solution.
3, prepare cyclohexanone and the pure technology of ring according to claim 1 is described from cyclohexane, it is characterized in that, it is to be 80 °-155 ° in temperature that described homogeneous catalysis is decomposed, under the pressure 100KPa-1200KPa condition, be that the oil soluble transition metal salt of 0.3-1000ppm is made the catalyst treatment oxidation mixture with concentration.
According to claim 1 or 2 or 3 described preparation technologies, it is characterized in that 4, the transition metal salt that is used as catalyzer is cobalt salt or chromic salts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110939A CN1063419C (en) | 1994-04-22 | 1994-04-22 | process for preparing cyclohexanol and cyclohexanone from cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110939A CN1063419C (en) | 1994-04-22 | 1994-04-22 | process for preparing cyclohexanol and cyclohexanone from cyclohexane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1105970A true CN1105970A (en) | 1995-08-02 |
| CN1063419C CN1063419C (en) | 2001-03-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110939A Expired - Lifetime CN1063419C (en) | 1994-04-22 | 1994-04-22 | process for preparing cyclohexanol and cyclohexanone from cyclohexane |
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| CN (1) | CN1063419C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079388C (en) * | 1998-11-12 | 2002-02-20 | 肖藻生 | Method for preparing cyclohexanol and cyclohexanone |
| 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 |
| CN102452968A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing methyl cyclohexyl hydrogen peroxide with methylcyclohexane subjected to aerobic oxidation |
| CN102617278A (en) * | 2012-02-24 | 2012-08-01 | 中国石油化工股份有限公司 | Method for preparing cyclohexanone and cyclohexanol by resolving cyclohexyl hydroperoxide |
| CN102627542A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Process for preparing hexanaphthene and cyclohexanone with cyclohexane serving as raw material |
| CN102656143A (en) * | 2009-12-17 | 2012-09-05 | 罗地亚经营管理公司 | Method for oxidizing hydrocarbons with oxygen |
| WO2013143211A1 (en) * | 2012-03-31 | 2013-10-03 | Xiao Zaosheng | Production process for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation |
| CN103987452A (en) * | 2011-12-07 | 2014-08-13 | 帝斯曼知识产权资产管理有限公司 | Process for the production of a mixture comprising cyclohexanol and cyclohexanone |
| CN107400038A (en) * | 2016-05-20 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and cyclohexanol |
| CN108602736A (en) * | 2015-12-07 | 2018-09-28 | 宇部兴产株式会社 | Manufacture the method and its system of ketone and/or alcohol |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296333C (en) * | 2004-07-13 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for catalytic decomposition of cyclohexane hydroperoxide |
| CN101172931B (en) * | 2006-11-01 | 2011-11-16 | 肖藻生 | Improved process for producing cyclohexanol and pimelinketone |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4503257A (en) * | 1983-05-18 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Cyclohexyl hydroperoxide decomposition process |
| NL8802592A (en) * | 1988-10-21 | 1990-05-16 | Stamicarbon | METHOD FOR PREPARING A K / A MIXTURE |
-
1994
- 1994-04-22 CN CN94110939A patent/CN1063419C/en not_active Expired - Lifetime
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| CN1079388C (en) * | 1998-11-12 | 2002-02-20 | 肖藻生 | Method for preparing cyclohexanol and cyclohexanone |
| 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 |
| CN102656143A (en) * | 2009-12-17 | 2012-09-05 | 罗地亚经营管理公司 | Method for oxidizing hydrocarbons with oxygen |
| CN102656143B (en) * | 2009-12-17 | 2015-09-09 | 罗地亚经营管理公司 | With the method for dioxygen oxidation hydrocarbon polymer |
| CN102452968A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing methyl cyclohexyl hydrogen peroxide with methylcyclohexane subjected to aerobic oxidation |
| CN103987452A (en) * | 2011-12-07 | 2014-08-13 | 帝斯曼知识产权资产管理有限公司 | Process for the production of a mixture comprising cyclohexanol and cyclohexanone |
| CN103987452B (en) * | 2011-12-07 | 2016-02-24 | Capiii有限公司 | Comprise the preparation method of the mixture of cyclohexanol and cyclohexanone |
| CN102617278A (en) * | 2012-02-24 | 2012-08-01 | 中国石油化工股份有限公司 | Method for preparing cyclohexanone and cyclohexanol by resolving cyclohexyl hydroperoxide |
| CN102627542A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Process for preparing hexanaphthene and cyclohexanone with cyclohexane serving as raw material |
| EP2821384A4 (en) * | 2012-03-31 | 2015-03-18 | Zaosheng Xiao | Production process for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation |
| WO2013143211A1 (en) * | 2012-03-31 | 2013-10-03 | Xiao Zaosheng | Production process for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation |
| US9150481B2 (en) | 2012-03-31 | 2015-10-06 | Zaosheng Xiao | Process for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation |
| CN108602736A (en) * | 2015-12-07 | 2018-09-28 | 宇部兴产株式会社 | Manufacture the method and its system of ketone and/or alcohol |
| CN107400038A (en) * | 2016-05-20 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and cyclohexanol |
| 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 |
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