CN1079388C

CN1079388C - Method for preparing cyclohexanol and cyclohexanone

Info

Publication number: CN1079388C
Application number: CN98112730A
Authority: CN
Inventors: 肖藻生
Original assignee: Individual
Current assignee: Individual
Priority date: 1998-11-12
Filing date: 1998-11-12
Publication date: 2002-02-20
Anticipated expiration: 2018-11-12
Also published as: CN1253938A

Abstract

The present invention discloses a method for preparing cyclohexanol and cyclohexanone. When a transition metal salt is used to decompose oxidative mixture containing cyclohexyl hydrogen peroxide, the present invention adopts the external circulation of alkali lye and a static mixer, and controls the flow rate of the external circulation of the alkali lye and makes the flow rate of the alkali lye 0.2 to 1 time that of the oxidative mixture. After a material passes through the static mixer, the grain size of a dispersed phase droplet is from 1 to 100 mu m, so that the cyclohexyl hydrogen peroxide in the cyclohexane oxidative liquor can be decomposed with high conversion to obtain cyclohexanol and cyclohexanone.

Description

A kind of method for preparing hexalin and pimelinketone

The present invention relates to a kind of cyclohexyl hydroperoxide and decompose improving one's methods of production hexalin and pimelinketone.

CN88105772X, CN94110939.9, CN96118441.8, US5233092A, the JP2067789 patent disclosure preparation technology of hexalin and pimelinketone.Preparation technology comprises (A) gas cyaniding hexanaphthene with molecule-containing keto in oxidation reactor, generates the cyclohexane oxidation mixture that contains cyclohexyl hydroperoxide; (B) the cyclohexane oxidation mixture is carried out decomposition reaction, make cyclohexyl hydroperoxide wherein decompose generation hexalin and pimelinketone; (C) use rectifying separation, obtain hexanaphthene, hexalin and pimelinketone.The hexanaphthene Returning oxidation reactor, hexalin and pimelinketone become product.The shortcoming of above-mentioned technology is: the yield that hexanaphthene finally changes into hexalin and pimelinketone is low, and especially the yield that contained cyclohexyl hydroperoxide decomposition generates hexalin and pimelinketone in the cyclohexane oxide solution is low.Be in the homogeneous catalysis decomposition technique of catalyzer with oil soluble cobalt salt and/or chromic salts, it is the acidic precipitation thing of core component that cobalt salt and/or chromic salts generate easily with hexanodioic acid cobalt and/or chromium, disabling facility and pipeline, and catalytic activity is low, the decomposition reaction transformation efficiency is low, thereby yield is low.Be that catalyst activity is low in the acid heterogeneous decomposition technique of catalyzer with aqueous solution cobalt salt and/or aqueous solution of chromium salt, catalyst levels is big, and the decomposition reaction transformation efficiency is low, thereby yield is low.In the traditional alkaline heterogeneous catalysis decomposition technique that sodium hydroxide and/or aqueous sodium carbonate with aqueous solution cobalt salt and/or chromic salts are catalyzer, cyclohexyl hydroperoxide is decomposition and inversion one-tenth acid easily under strong alkaline condition, makes the yield of decomposition reaction generation hexalin and pimelinketone low.

The novel process that the purpose of this invention is to provide the preparation of a kind of hexalin and pimelinketone, the yield that makes cyclohexane oxidation process produce hexalin and pimelinketone greatly improves, especially improve cyclohexyl hydroperoxide in the cyclohexane oxide solution and decompose the yield that generates hexalin and pimelinketone, reach to reduce and consume the purpose that reduces cost.

The object of the present invention is achieved like this: (A) under temperature 150-185 ℃, pressure 0.8Mpa-1.95Mpa condition, generate the oxidation mixture that contains cyclohexyl hydroperoxide with the gas cyaniding hexanaphthene of molecule-containing keto; For under identical cyclohexane oxidation transformation efficiency, improve the content of cyclohexyl hydroperoxide, reduction pimelinketone etc. are the content of deep oxidation product easily, improve the yield of oxidation, can in hexanaphthene, add 0.1ppm 1-hydroxy ethylidene-1, the catalytic decomposition activity of 1-bisphosphonates passivation trace metal ion and reactor wall; (B) under temperature 50-100 ℃, pressure 0.01Mpa-1.5Mpa condition, with transition metal salt decomposing cyclohexylhdroperoxide in the presence of alkali metal hydroxide aqueous solution, generation hexalin and pimelinketone; (C) with rectifying tower separating benzene-cyclohexane, hexalin and pimelinketone.The invention is characterized in transition metal salt and decompose when containing the oxidation mixture of cyclohexyl hydroperoxide, be to adopt alkali lye outer circulation and static mixer, and the flow of control alkali lye outer circulation is 0.2-1 times of the oxidation mixture flow, material by static mixer after the dispersed phase drop granularity be 1-100 μ m, the transition metal salt concentration range is the 0.1-50ppm of alkali lye weight; And decomposed for two steps and carry out, the low basicity of the 1st step control, second step was improved basicity again, OH in alkali lye when for example the 1st step decomposed ^-Concentration is 0.1-0.5mol/L, OH in alkali lye when the 2nd step decomposed ^-Concentration is 0.5-1.5mol/L.The alkali lye that the 1st step decomposed also can be selected NaCO for use ₃The aqueous solution, it is the NaOH aqueous solution that the 2nd step decomposed, and reaches with this and improves the purpose that the alcohol ketone yield reduces material consumption.

Cyclohexane oxide solution contains hexalin 0.8-2.5%, pimelinketone 0.3-1.5%, cyclohexyl hydroperoxide 0.8-3.4%, organic acids such as hexanodioic acid, ester and the light constituent reorganization byproduct 0.5-2% altogether that grades, other 95-96% is a hexanaphthene, light constituent is meant that than the low-boiling byproduct of pimelinketone, heavy constituent are meant the byproduct higher than hexalin boiling point.The most traditional facture of this cyclohexane oxide solution is to adopt the NaOH aqueous solution and cyclohexane oxide solution together to enter saponification column, carries out neutralization, the saponification of ester and the decomposition of cyclohexyl hydroperoxide of acid in saponification column; The 50-60 age, because saponification column temperature height, the basicity height, alkali lye viscosity is big, and it is low to obtain hexalin pimelinketone yield after cyclohexyl hydroperoxide decomposes in saponification column, and cyclohexyl hydroperoxide mostly decomposes byproducts such as generation acid under operating mode at that time.The eighties, Holland DSM N. V. applied for the 0092867A1 European patent, when handling this cyclohexane oxide solution with the alkali aqueous solution that contains the 1PPM transition metal ion, it is characterized in that controlled temperature is 70 ℃-115 ℃.Be so-called low-temperature decomposition technology, they industrial use be three placed in-line bands stir continuously in and decomposition reactor.Du pont company application in 1993 the US5206441 patent, adopt the whirling motion mixing tank when it is characterized in that cyclohexane oxide solution and containing the mixing of alkali aqueous solution of 1PPM transition metal.More than these technology on full scale plant, adopt, the molar yield that cyclohexyl hydroperoxide decompose to generate the hexalin pimelinketone all is lower than 84%.We are by the research to reaction mechanism, think that cyclohexane oxide solution is when containing transition metal salt alkali aqueous solution catalytic decomposition, cyclohexyl hydroperoxide at first is extracted into the buck phase, in alkali aqueous phase generation catalytic decomposition, generate hexalin and pimelinketone, hexalin with after pimelinketone generates again collection get back to hexanaphthene mutually in.To get back to hexanaphthene mass transfer velocity mutually be a slowest step because above decomposition method does not fully take into account hexalin and pimelinketone collection, thus the hexalin pimelinketone at alkali aqueous phase concentration height, side reaction speed is fast, makes that to decompose yield low.

We recycle by alkali lye, have strengthened the flow of alkali lye, make buck bring up to 0.2-1 with comparing of cyclohexane oxidation liquid phase mutually, and preferably comparing is 0.5, when the flow of oxidation mixture and alkali lye is by static mixer in other words, is in a ratio of 2 to 1; Especially static mixer is adopted in the mixing of buck phase and cyclohexane oxidation liquid phase, and buck phase and cyclohexane oxidation liquid phase were mixed in the extremely short time, and making dispersed phase particles diameter wherein is 1-100 μ m.Material is by behind the static mixer, and preferred disperse phase granularity is 1-10 μ m.By above improvement, the decomposition yield of cyclohexyl hydroperoxide in the cyclohexane oxide solution is brought up to about 95%, below in conjunction with embodiment the present invention is described in detail.

Embodiment 1: present embodiment uses the technical process in the synoptic diagram 1, in 30 liters of cyclohexane oxide solution decomposition reactors 4 of continuously stirring, from 180 liters of the cyclohexane oxide solutions of pipeline 1/time, from 30 liters of the NaOH aqueous solution of pipeline 2/time and from 60 liters of the circulation alkali liquors of pipeline 5/time, after static mixer M mixing, enter the decomposition reaction that cyclohexyl hydroperoxide takes place in the decomposition reactor 4.85 ℃ of control decomposition temperatures, decomposition pressure 0.3Mpa.Cyclohexane oxide solution is composed as follows: hexalin 0.8%, pimelinketone 0.336%, cyclohexyl hydroperoxide 3.4%, acid 0.15%, ester 0.134%, other is hexanaphthene.The NaOH aqueous solution in the pipeline 2 is composed as follows: contain Colppm, OH ^-Concentration 1mol/L, admittedly contain thing 17%, other is a water.Material is by behind the static mixer, and the dispersed phase particles diameter is 1-100 μ m.The agitator revolution is 200 rev/mins.Carry out chemical analysis from pipeline 3 samplings, obtain cyclohexyl hydroperoxide rates of decomposing and transforming 95%, decompose yield 94%.

The comparative example 1:

This comparative example uses the technical process among Fig. 2, in 30 liters of decomposition reactors 4 of continuously stirring, from 180 liters of the cyclohexane oxide solutions of pipeline 1/time and from 30 liters of the NaOH aqueous solution of pipeline 2/time, 85 ℃ of decomposition temperatures, decomposition pressure 0.3Mpa, under 200 rev/mins of the agitator revolutions, the decomposition reaction of cyclohexyl hydroperoxide takes place.Material is formed identical with embodiment 1, does not just adopt static mixer and carries out the alkali lye outer circulation, and alkali lye directly adds in the decomposition reactor 4, by mixing.The result is from pipeline 3 sampling analysis, a cyclohexyl hydroperoxide rates of decomposing and transforming 70-80%, and decomposing yield is 84%.

Embodiment 2:

Present embodiment uses the technical process among Fig. 3, decomposing for two steps carries out, the 1st step is in 50 liters of cyclohexane oxide solution decomposition reactors 4 of continuously stirring, from 240 liters of the cyclohexane oxide solutions of pipeline 1/time, from 20 milliliters of the Cobaltous diacetate aqueous solution that contains 0.1%Co of pipeline 6/time, from 20 liters of the alkali lye of pipeline 2/time and from 100 liters of the alkali lye of pipeline 5/time mix by static mixer M1 after, enter reactor 4, about 83 ℃-85 ℃ of the pressure 0.15Mpa (absolute pressure) of controlling reactor 4 and temperature, cyclohexane oxide solution is formed identical with embodiment 1, OH in the alkali lye of pipeline 2 ^-Concentration is 0.75mol/L, salt 15%, and other is a water, OH in the outer circulation alkali lye of pipeline 5 ^-Concentration is 0.25mol/L, and salt is 17%, and other is a water.In decomposition reactor 4, rates of decomposing and transforming is about 90%, and reaction mixture is pressurized to 0.8Mpa through pipeline 3 usefulness pumps, and layering separates in separator, and lower floor's alkali lye major part is circulated to decomposition reactor 4 by pipeline 5, per hour discharges about 4 liters with salkali waste through pipeline 14.Small part alkali lye enters second decomposition reactor 10 in company with the hexanaphthene organic phase through pipeline 8 in addition, carrying out for second step decomposes, this part material and among static mixer M2, mix from the 4 liters/stylish alkali lye that contains NaOH 12% of pipeline 9, decomposition temperature rises to about 90 ℃, the cyclohexyl hydroperoxide decomposition and inversion is near 100%, the total recovery that two steps decomposed is 95%, reaction mixture is after piping 11 usefulness pumps are pressurized to 1.5Mpa, layering separates in separator 13, lower floor's alkali lye is circulated in the decomposition reactor 4 through pipeline 2, upper strata hexanaphthene organic phase is decyclization hexane rectifying tower after pipeline 12 heat exchange, and rectifying separation obtains hexanaphthene, pimelinketone and hexalin.

The comparative example 2:

This comparative example uses the technical process among Fig. 4, in 50 liters of cyclohexane oxide solution decomposition reactors 4 of continuously stirring, from 240 liters of the cyclohexane oxide solutions of pipeline 1/time, from 20 milliliters of the aqueous solution of the Cobaltous diacetate that contains Co0.1% of pipeline 6/time, from 30 liters of the circulation alkali liquors of pipeline 2/time and from 6 liters of the new alkali lye that contains NaOH12% of pipeline 9/time, after entering decomposition reactor 4 respectively, mix reaction through agitator, controlled temperature 85-90 ℃, pressure 0.3Mpa, the rates of decomposing and transforming of cyclohexyl hydroperoxide is 50%-95% in decomposition reactor 4, be pressurized to 0.8Mpa through pipeline 3 usefulness pumps then, enter in

decomposition reactor

7 and 8, under agitator stirs, continue reaction, the cyclohexyl hydroperoxide rates of decomposing and transforming is near 100%, but decomposes the yield only 84% that generates hexalin and pimelinketone.The reaction mixture material enters in the layering separator 13 after pipeline 11 usefulness pumps are pressurized to 1.5Mpa, and the upper strata contains the hexanaphthene organic phase of alcohol ketone and remove alkane rectification after heat exchange.6 liters/hour of lower floor's alkali lye are done the waste lye discharging, and other about 30 liters/hour return in the decomposition reactor 4 as circulation alkali liquor.

Claims

1. method for preparing hexalin and pimelinketone comprises (A) under temperature 150-185 ℃, pressure 0.8Mpa-1.95Mpa condition, generates the oxidation mixture that contains cyclohexyl hydroperoxide with the gas cyaniding hexanaphthene of molecule-containing keto; (B) under temperature 50-100 ℃, pressure 0.01Mpa-1.5Mpa condition, with transition metal salt decomposing cyclohexylhdroperoxide in the presence of alkali metal hydroxide aqueous solution, generation hexalin and pimelinketone; (C) with rectifying tower separating benzene-cyclohexane, hexalin and pimelinketone, it is characterized in that decomposing when containing the oxidation mixture of cyclohexyl hydroperoxide with transition metal salt, be to adopt alkali lye outer circulation and static mixer, and the flow of control alkali lye outer circulation be the oxidation mixture flow 0.2-1 doubly, material by static mixer after the dispersed phase drop granularity be 1-100 μ m.

2. method according to claim 1 is characterized in that adding in the hexanaphthene 0.1ppml-hydroxy ethylidene-1,1-bisphosphonates.

3. method according to claim 1, the flow that it is characterized in that oxidation mixture and alkali lye are in a ratio of 2 to 1 during by static mixer.

4. method according to claim 1, it is characterized in that material passes through static mixer after, the dispersed phase drop granularity is 1-10 μ m.

5. method according to claim 1 is characterized in that alkali metal hydroxide OH in the 1st step decomposition reaction ^-Concentration be 0.1-0.5mol/L, the 2nd the step decomposition reaction in OH ^-Concentration be 0.5-1.5mol/L.

6. method according to claim 1 is characterized in that transition metal salt is cobalt salt or chromic salts.

7. method according to claim 1 is characterized in that the transition metal salt concentration range is the 0.1-50ppm of alkali lye weight.