公开(公告)号：GB849134A

公开(公告)日：1960-09-21

申请号：GB2599858

申请日：1958-08-13

Applicant: BASF AG

Inventor： SIMON WALTER ,  WALDMANN HANS JOACHIM ,  GOEHRE OTTO

Abstract: In a process for the production of cycloaliphatic alcohols and ketones, by the oxidation of cycloaliphatic hydrocarbons in the liquid phase with oxygen or oxygen-containing gases in a plurality of successive oxidation-vessels, the oxidation-mixture from the last vessel is washed with fresh water to remove monobasic acids formed during the oxidation, the washing-water is separated from the oxidation-mixture, the washing-water is then used, wholly or partly, for washing the intermediate oxidation-mixture from each of the preceding oxidation-stages, and the final oxidation-mixture is submitted to distillation, for the separation of the unreacted cycloaliphatic hydro-carbon and the individual oxidation products. The oxidation-mixture is preferably washed with aqueous alkali hydroxide or carbonate solution before the distillation. Organic acids can be recovered from the washing-water and from the aqueous alkaline solution. The process may be used for the oxidation of cyclohexane in order to produce cyclohexanone and cyclohexanol; it may also be used for the oxidation of methyl-cyclohexane and cyclooctane. The oxidation is advantageously carried out at a temperature of 130 DEG -150 DEG C., a pressure of 3 to 30 atm., and in the presence of an oxidation-catalyst, such as cobalt naphthenate. The gaseous and vaporous constituents of the intermediate oxidation-mixtures are preferably subjected to water-washing together with the liquid constituents; the gaseous streams are then combined and cooled to recover unreacted cycloaliphatic hydrocarbon. The gaseous stream is finally washed with the liquid oxidationproduct, i.e., the final oxidation-mixture from which the unchanged hydrocarbon has been removed by distillation. Specification 776,803 is referred to.

公开(公告)号：GB918900A

公开(公告)日：1963-02-20

申请号：GB1581461

申请日：1961-05-02

Applicant: BASF AG

Inventor： WALDMANN HANS JOACHIM ,  HOFFMANN HERWIG

IPC: C07C45/00 ,  C07C45/82

Abstract: Cyclohexane is oxidised in liquid phase with an oxygen-containing gas at 120-170 DEG C. and at a pressure up to 70 atmospheres; the oxidation mixture containing 30-98% by weight of cyclohexane is contacted with a 10-30% aqueous solution of an alkali hydroxide or carbonate at 60-150 DEG C. for 2-60 minutes; the aqueous phase is separated from the oxidation mixture; the cyclohexane is distilled off from the oxidation mixture until the content thereof is less than 20% by weight; alkali hydroxide or carbonate is added in an amount corresponding to 0.20-0.95 equivalents of the esters contained in the oxidation mixture and the mixture is then heated for 0.1-10 minutes at 130-160 DEG C.; pure cyclohexanol and pure cyclohexanone are then recovered by fractional distillation of the oxidation mixture, preferably under reduced pressure without previous separation of the alkali compound. Oxidation may be effected in two or three stages, and an oxidation catalyst such as cobalt naphthenate may be present. Water formed during the oxidation may be left in the reaction mixture or distilled off continuously. After the oxidation or after one or more oxidation stages, the reaction mixture may be subjected to water washing e.g. at 60-120 DEG C. If desired, the cyclohexanol obtained may be dehydrogenated and converted to cyclohexanone by heating in gas phase with a catalyst such as an oxide of Cu, Cr, Ni, Zn, Mo, or V. Specifications 776,803 and 815,162 are referred to.

公开(公告)号：GB852523A

公开(公告)日：1960-10-26

申请号：GB3046758

申请日：1958-09-24

Applicant: BASF AG

Inventor： WALDMANN HANS JOACHIM ,  PLAUTH ERNST ,  GOEHRE OTTO

IPC: B01J19/24

Abstract: In a process for producing cycloaliphatic alcohols and ketones by the oxidation of cycloaliphatic hydrocarbons, such as cyclohexane, methyl cyclohexane or cyclo-octane, in the liquid phase by means of oxygen-containing gas, in the presence or absence of a catalyst, the oxidation is carried out, at temperatures of 100 DEG to 180 DEG C. under a pressure of 3 to 50 atm., in a series of reactors each provided with means for circulating the oxidation-mixture therein; the mixture discharged from the last reactor is washed with water and then wholly or partly decompressed; the decompressed liquid is then passed through heat-exchangers wherein it is heated by the hot compressed mixture leaving each reactor, whereby the unreacted hydrocarbon is partially vaporized from the decompressed liquid; and the unreacted hydrocarbon is finally separated by distillation from the cycloaliphatic alcohol and ketone produced by oxidation. In the apparatus shown, there are two reactors 5 and 18. Cyclohexane is fed through pipe 1 and heat-exchangers 2 and 3, in which it is preheated to 80 DEG C., next through gas-heated preheater 4, where it is raised to 100 DEG C., and then enters reactor 5, which is provided with an insert-tube to cause circulation. Air and a solution of cobalt naphthenate in cyclohexane are pumped through pipe 6 into reactor 5. A temperature of 140 DEG C. and a pressure of 25 atm. are maintained in the reactor. Oxidation-mixture, leaving the top of the reactor, is mixed with water from pipe 11 and then flows through heat-exchanger 9, wherein it gives up heat to washed, decompressed product. The partially-cooled oxidation-mixture now flows through heat-exchanger 3, wherein it gives up further heat to the feed. The oxidation-mixture, now at 80 DEG C. is passed into separator 13 from which the water-layer is withdrawn via pipe 15. The washed oxidation-mixture is reheated to 100 DEG C. in preheater 17, and is then introduced into reactor 18, wherein oxidation takes place in the same manner as in reactor 5. The hot oxidation-mixture is mixed with water from pipe 11 and then passes through heat-exchanger 22, where it gives up heat to the washed, decompressed product which has already passed through heat exchanger 9. The partiallycooled oxidation-mixture then flows through heat-exchanger 2 into separator 25. The mixture is next mixed with fresh water, and passed to separator 30. The washing-water, withdrawn from separator 30, is supplied to line 11. The oxidation-mixture is next washed with 15% caustic soda solution, and finally with water again. The washed oxidation-mixture is withdrawn from separator 36 through pipe 38, decompressed to atmospheric-pressure by valve 39, and then passed via heat-exchangers 9 and 22 to the distillation plant where the unreacted cyclohexane is separated. Cyclohexanone and cyclohexanol are obtained by further distillation. Specification 815,162 is referred to.

公开(公告)号：GB913000A

公开(公告)日：1962-12-12

申请号：GB4295960

申请日：1960-12-14

Applicant: BASF AG

Inventor： POEHLER GUENTER ,  WALDMANN HANS JOACHIM ,  CORR HUBERT

IPC: C07C45/82

Abstract: Pure cyclohexanone is separated from mixtures, obtained by the oxidation of cyclohexane with oxygen followed by distilling off excess cyclohexane, by submitting the cyclohexane-free mixture to a multi-stage rectification process, one stage being carried out under a pressure of 300 mm. Hg. absolute to 5 atmospheres in order to remove low-boiling impurities such as amyl alcohol and aliphatic ketones, and another stage being carried out at a pressure of 1 to 300 mm. Hg. absolute whereby cyclohexanone is separated from cyclohexanol. These two stages may be conducted in either sequence. The difference in pressure between the two stages is preferably at least 300 mm. Hg. In an example, cyclohexane is oxidised with air, using cobalt naphthenate as catalyst, the reaction being carried out at a temperature of 140 DEG C. and a pressure of 25 atm. The oxidation-mixture is washed with water, and then re-oxidized. The oxidation-product is washed with water, then with caustic soda solution, then with water again. Excess cyclohexane is then removed from the mixture by distillation. The mixture is then submitted to rectification in the apparatus shown in the Figure. The mixture is first rectified under a pressure of 30 mm. Hg. absolute in column 2, which has sixty bubbletrays. With a reflux-ratio of 3:1 and a headtemperature of 63 DEG C., a cyclohexanonefraction is withdrawn through pipe 3 and condensed. The condensate is rectified under atmospheric pressure in column 4 using a reflux-ratio of 9 : 1. Low-boiling impurities are withdrawn through pipe 5. Cyclohexanone is withdrawn from the base of column 4, and is submitted to final purification in column 7, which is operated under a pressure of 30 mm. Hg. absolute. Pure cyclohexanone is obtained at the top of column 7. The residue withdrawn from the base of column 7 is returned to column 2 through pipe 10. The cyclohexanol fraction, withdrawn from the base of column 2, is distilled in column 12 at a pressure of 30 mm. Hg. absolute. Cyclohexanol, obtained as overhead-product from column 12, is passed over a copper catalyst, deposited on silicic acid, in dehydrogenator 17, which is maintained at 280 DEG to 320 DEG C. The cyclohexanone from the dehydrogenator may be passed via pipe 18 to column 2, or it may be freed from volatile by-products in column 20 and then passed via pipe 21 to column 7. In another example, the oxidation-mixture, already freed from cyclohexane, is first freed from low-boiling impurities by rectification under atmospheric pressure, and is then rectified at 30 mm. Hg. absolute to obtain pure cyclohexanone as distillate. Specifications 815,162 and 849,134 are referred to.

公开(公告)号：FR1288624A

公开(公告)日：1962-03-24

申请号：FR861034

申请日：1961-05-06

Applicant: BASF AG

Inventor： WALDMANN HANS JOACHIM ,  HOFFMANN HERWIG

公开(公告)号：FR1209534A

公开(公告)日：1960-03-02

申请号：FR1209534D

申请日：1958-08-13

Applicant: BASF AG

Inventor： SIMON WALTER ,  WALDMANN HANS JOACHIM ,  GOEHRE OTTO

IPC: C07C45/33