CN1184097A - Preparation process of cyclohexanol and cyclohexanone - Google Patents
Preparation process of cyclohexanol and cyclohexanone Download PDFInfo
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Abstract
The preparation process includes the production of cyclohexane oxide mixture containing cyclohexyl hydrogen peroxide by using molecular oxygen containing gas to oxidize cyclohexane in oxidizing reactor; the decomposition of the said oxide mixture into cyclohexanol and cyclohexanone; and the rectification to separate cyclohexane, cyclohexanol and cyclohesanone. It features that in the decomposition of cyclohesane oxide mixture containing cyclohexyl hydrogen peroxide, acid water solution of cobalt salt and/or chromium salt is used as catalyst.
Description
The present invention relates to the preparation technology of hexalin and pimelinketone.
CN88105772.X, CN94110939.9, CN95112470.6, US5233.092A discloses the preparation technology of hexalin and pimelinketone JP2067789 number.Production technique 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 decomposed, make cyclohexyl hydroperoxide wherein decompose generation hexalin and pimelinketone; (C) use rectifying separation, obtain hexanaphthene, hexalin and pimelinketone product, hexanaphthene Returning oxidation reactor.
The shortcoming of above-mentioned technology is: the selectivity that hexanaphthene finally changes into hexalin and pimelinketone is low, and especially the selectivity that contained cyclohexyl hydroperoxide decomposition generates hexalin and pimelinketone in the cyclohexane oxidation mixture is low; Be in the homogeneous decomposition technology of catalyzer with oil soluble cobalt salt and/or chromic salts, it is the acidic precipitation thing of core that cobalt salt and/or chromic salts generate easily with hexanodioic acid cobalt and/or chromium, disabling facility and pipeline, and it is low to decompose yield, generates heavy constituent by products (X oil) when cyclohexyl hydroperoxide decomposes easily.
Be in the heterogeneous decomposition traditional technology of catalyzer with water soluble cobaltous salt and/or chromic salts, the employed aqueous solution all emphasizes it must is the aqueous solution of alkalescence, be that the aqueous solution is the alkali aqueous solution that contains NaOH, the concentration of NaOH in the aqueous solution is 1-18%, because the aqueous solution is alkalescence, cobalt salt and/or the chromic salts solubleness in alkali aqueous solution is very low, generally be lower than 1ppm, unnecessary cobalt and/or chromium all generate cobaltous hydroxide and/or chromium hydroxide precipitation, the catalysis cyclohexyl hydroperoxide generates hexalin and pimelinketone directed the decomposition effectively, cyclohexyl hydroperoxide is in the heterogeneous decomposition technique of alkalescence, decomposition and inversion becomes acid easily, 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 generate hexalin and pimelinketone greatly improves, and reaches to reduce to consume the purpose that reduces cost.
The object of the present invention is achieved like this.(A) in oxidation reactor, 150 ℃-183 ℃ of controlled temperature under the gauge pressure 0.8-1.95Mpa condition, with the gas cyaniding hexanaphthene of molecule-containing keto, generate the cyclohexane oxidation mixture that contains cyclohexyl hydroperoxide; (B) the cyclohexane oxidation mixture that will contain cyclohexyl hydroperoxide decomposes, and makes it to generate hexalin and pimelinketone; (C) with rectifying separation hexanaphthene, hexalin and pimelinketone product, hexanaphthene Returning oxidation reactor; The invention is characterized in and decompose when containing the cyclohexane oxidation mixture of cyclohexyl hydroperoxide, use the catalyzer of the acidic aqueous solution of water soluble cobaltous salt and/or chromic salts as decomposition reaction.
In the acidic aqueous solution catalyzer, the concentration of cobalt and/or chromium is 100-10000ppm, and cobalt and/or the chromium concentration in the aqueous solution is during less than 100ppm, and catalytic activity descends, cobalt and/or the chromium concentration in the aqueous solution has increased the loss of cobalt salt and chromic salts during greater than 10000ppm.Owing to contain acetic acid, propionic acid, hexanodioic acid etc. in the cyclohexane oxidation mixture, after cobalt salt and/or aqueous solution of chromium salt add decomposing system, promptly become the acidic aqueous solution of cobalt salt and/or chromic salts, in acidic aqueous solution, cobalt and/or chromium exist with ion condition shape, can not generate cobaltous hydroxide and/or chromium hydroxide precipitation.Cobalt and/or chromium are preferably 500-2000ppm in the concentration of aqueous phase in aqueous catalyst solution.The employed water-soluble salt of catalyzer is Cobaltous diacetate and/or rose vitriol, Xiao Suangu, chromium acetate, chromic trioxide etc.
The add-on of aqueous solution catalyzer also is very important, if add-on is very little the time, for example, the amount of aqueous catalyst solution is less than 1% o'clock of cyclohexane oxidation mixture amount, because the cyclohexane oxidation mixture is dry water-free, after moisture content in the catalyzer is dissolved in the cyclohexane oxidation mixture, cobalt salt and/or chromic salts are separated out, become solids and block pipeline and equipment, therefore the add-on of the aqueous solution of catalyzer cobalt salt and/or chromic salts is the 1-50% of cyclohexane oxidation volume of mixture flow, is preferably 4-30%.When the aqueous catalyst solution add-on is too big, corresponding large equipment and the pipeline of adding, investment is increased.The service temperature that the cyclohexane oxidation mixture process is decomposed in cobalt salt and/or the heterogeneous catalysis of chromic salts acidic aqueous solution is 100 ℃-160 ℃, pressure is 0.5-2.0MPa, pressure must guarantee not seethe with excitement under the decomposition temperature, when being lower than 100 ℃, decomposition reaction velocity is too slow, need to increase the reaction times of decomposing, strengthen the size of relevant device, investment is increased; When being higher than 160 ℃, decomposition reaction velocity is too fast, and the side reaction meeting increases, and yield is reduced, and the optimal operations temperature is 120-130 ℃; The contact reacts time of aqueous catalyst solution and cyclohexane oxidation mixture is 3 minutes to 180 minutes, and the best reaction times is 15 minutes to 40 minutes.
In order to guarantee that inorganic phase catalyst cobalt salt and/or aqueous solution of chromium salt contact with the thorough mixing of organic phase cyclohexane oxidation mixture, use static mixer during mixing, make aqueous catalyst solution be dispersed into the particle of 1 μ m to 500 μ m, be dispersed in the cyclohexane oxidation mixture, like this, decomposition reaction velocity can be accelerated, and the yield that decomposition reaction generates alcohol ketone can be improved.In duration of contact, guarantee water and hexanaphthene thorough mixing mutually in the entire reaction of decomposition reaction, can adopt the decomposition reactor of following current or adverse current, also can adopt the reactive tank of pipeline reactor or belt stirrer.Reaction mixture after decomposition reaction is finished enters settlement separator, upper organic phase be contain hexalin and pimelinketone hexanaphthene mutually, according to the finished product needs, wash, perhaps carry out buck and wash, perhaps directly carry out smart gold-plating, obtain hexanaphthene, hexalin and pimelinketone product, hexanaphthene returns the front oxidation reactor, proceeds oxidation.Lower floor is inorganic mutually for containing the acidic aqueous solution of cobalt salt and/or chromic salts, and these aqueous solution major parts are returned decomposition reactor and done catalyst recirculation and use, small part can discharger outside, otherwise processed therefrom reclaims cobalt salt, chromic salts and hexanodioic acid etc.
Implement effect of the present invention: after implementing the present invention, the molar yield that cyclohexane oxidation prepares hexalin and pimelinketone is brought up to 85-88% from the 72-82% of original technology.
Have five accompanying drawings, wherein Fig. 1 is the small test setting drawing of embodiment 1-6, Fig. 2-the 5th, and the improved process flow sheet of a few cover full scale plants, each figure is described as follows:
Fig. 1: 1, N2 gas cylinder; 2, decomposition reactor; 3, thermometer; 4, tensimeter; 5, under meter.
Fig. 2: 1, the cyclohexane oxidation mixed solution that comes from oxidation reactor; 2, medial launder; 3, decomposition reaction tower; 4, separator 1; 5, fresh Cobaltous diacetate aqueous solution catalyzer; 6, the new alkali lye of 12%NaOH; 7, waste lye; 8, separator 2; 9, separator 3; 10, remove alkane tower material.
Fig. 3: 1, the cyclohexane oxidation mixed solution that comes from oxidation reactor; 2, medial launder; 3, decomposed solution separator; 4, acid spent catalyst outlet; 5, decompose pipeline reactor; 6, new alkali lye; 7, neutralization reactor; 8,9,10, alkali separator; 11, salkali waste outlet; 12, heat exchanger; 13, toward alkane 1 tower material; 14, alkane 3 towers; 15, thick alcohol ketone; 16, hexanaphthene.
Fig. 4: 1, the cyclohexane oxidation mixed solution that comes from oxidation reactor; 2, heat exchanger; 3,4, decomposition reactor; 5, the fresh Cobaltous diacetate aqueous solution; 6, decomposed solution separator; 7, neutralization reactor; 8, new alkali lye; 9,10,11, alkali separator; 12, waste lye; 13, spent catalyst liquid.
Fig. 5: 1, the cyclohexane oxidation mixed solution that comes from oxidation reactor; 2, heat exchanger; 3, raw catalyst; 4, decomposed solution separator; 5, spent catalyst liquid outlet; 6, upgrading tower; 7, hexanaphthene; 8, spissated mixture.
Below in conjunction with embodiment the present invention is described in detail:
Embodiment 1:
In the device of Fig. 1, add cyclohexane oxidation mixture 300ml, add the Cobaltous diacetate aqueous solution 150ml that contains cobalt 2000ppm, fill N
2To the 0.6MPa gauge pressure, and logical N
2Stirred in gas 500ml/ minute, and heated up, reacted 60 minutes down at 110 ℃, decrease temperature and pressure, sample thief is analyzed:
The cyclohexane oxidation mixture contains acid 0.21%, and ester 0.16% crosses 3.12%, ketone 0.45%, and alcohol 0.71%, other is a hexanaphthene.Organic phase sample contains acid 0.11% after the decomposition reaction, and ester 0.16% crosses 0.41%, ketone 1.53%, and alcohol 2.19%, other is mainly hexanaphthene; Decompose the back aqueous sample and contain acid 0.21%, contain a small amount of alcohol, ketone, mistake, alkane, contain still 2000ppm of cobalt.Calculating the decomposition reaction transformation efficiency is 86.9%, and yield is 110.5%, and molecular yield surpasses 100%, the atomic oxygen of emitting when decomposing is described, oxidized part hexanaphthene.
Embodiment 2:
In the device of Fig. 1, add cyclohexane oxidation mixture 300ml, the cyclohexane oxidation mixture contains acid 0.21%, and ester 0.16% crosses 3.12%, ketone 0.45%, alcohol 0.71%, other is considered as hexanaphthene, adds the Cobaltous diacetate aqueous solution 150ml that contains cobalt 1000ppm again, fills N
2To the 0.6MPa gauge pressure, continue logical N
2Stirred in gas 500ml/ minute, and heated up, reaction is 15 minutes under 120 ℃ temperature, decrease temperature and pressure is poured reacted material into separating funnel, gets the upper oil phase analysis, contain acid 0.11%, ester 0.16% crosses 0.83%, ketone 1.33%, alcohol 1.94%, other is a hexanaphthene, the lower layer of water facies analysis, contain acid 0.21% and a small amount of alcohol, ketone, mistake, alkane, contain still 1000ppm of cobalt.
Calculating rates of decomposing and transforming is 73.4%, and decomposing yield is 109.8%.
Embodiment 3:
In the device of Fig. 1, add cyclohexane oxidation mixture 300ml, the cyclohexane oxidation mixture contains acid 0.21%, and ester 0.16% crosses 3.12%, ketone 0.45%, alcohol 0.71%, other is considered as hexanaphthene.Add the cobalt sulfate solution 150ml that contains cobalt 500ppm again, fill N
2To the 0.7MPa gauge pressure, continue logical N
2Stirred in gas 500ml/ minute, and heated up, reaction is 30 minutes under 130 ℃ temperature, decrease temperature and pressure is poured reacted material into separating funnel, gets the upper oil phase analysis, contain acid 0.11%, ester 0.14% crosses 0.2%, ketone 1.59%, alcohol 2.32%, other is considered as hexanaphthene, takes off a layer water analysis, contain acid 0.21% and a small amount of alcohol, ketone, mistake, alkane, contain cobalt 500ppm.Calculating rates of decomposing and transforming is 93.6%, and decomposing yield is 108.1%.
Embodiment 4:
In the device of Fig. 1, add cyclohexane oxidation mixture 300ml, the cyclohexane oxidation mixture contains acid 0.21%, and ester 0.16% crosses 3.12%, ketone 0.45%, alcohol 0.71%, other is considered as hexanaphthene.Adding has recycled 6 times the Cobaltous diacetate aqueous solution 150ml that contains cobalt 1000ppm again, fills N
2To the 0.7MPa gauge pressure, continue logical N
2Stirred in gas 500ml/ minute, and heated up, reaction is 30 minutes under 130 ℃ temperature, and decrease temperature and pressure is poured reacted material into separating funnel, gets the upper strata oil analysis, contains acid 0.14%, and ester 0.16% crosses 0.12%, ketone 1.71%, and alcohol 2.42%, other is a hexanaphthene; Take off a layer water analysis, contain acid 0.64% and a small amount of alcohol, ketone, alkane and cobalt 1000ppm, rates of decomposing and transforming is 96.2%, and decomposing yield is 115.8%.
Embodiment 5:
In the device of Fig. 1, add cyclohexane oxidation mixture 300ml to reactor, this cyclohexane oxidation mixture contains acid 0.21%, and ester 0.16% crosses 3.12%, ketone 0.45%, alcohol 0.71%, other is considered as hexanaphthene.Add the chromic acid that contains chromium 1000ppm again and do (CrO
3) aqueous solution 150m1, fill N
2To the 0.7MPa gauge pressure, continue logical N
2Stirred in 500ml/ minute, and heated up, reacted 20 minutes down at 125 ℃ with the resistance wire energising; Decrease temperature and pressure is poured reacted material into separating funnel, gets the upper oil phase analysis, contains acid 0.122%, and ester 0.16% crosses 0.05%, ketone 2.14%, and alcohol 1.55%, other is a hexanaphthene; Take off a layer water analysis, contain acid 0.16% and a small amount of alcohol, ketone, alkane and Cr1000ppm.Rates of decomposing and transforming is 98.3%, and decomposing molar yield is 97.08%.
Embodiment 6:
In the device of Fig. 1, add cyclohexane oxidation mixture 300ml to reactor, this cyclohexane oxidation mixture contains acid 0.21%, and ester 0.16% crosses 3.12%, ketone 0.45%, alcohol 0.71%, other is considered as hexanaphthene.Adding contains cobalt 500ppm and contains the Cobaltous diacetate of chromium 500ppm and the aqueous solution 150ml of chromium acetate again, fills N
2To the 0.7MPa gauge pressure, continue logical N
2Stirred in 500ml/ minute, and heated up, reacted 20 minutes down at 125 ℃ with the resistance wire energising; Decrease temperature and pressure is poured reacted material into separating funnel, gets the upper oil phase analysis, contains acid 0.109%, and ester 0.16% crosses 0.102%, ketone 2.09%, and alcohol 1.60%, other is a hexanaphthene; Take off a layer water analysis, contain acid 0.109% and a small amount of alcohol, ketone, alkane, other contains the nearly 500ppm of Co, the about 500ppm of Cr.Rates of decomposing and transforming is 97.0%, and decomposing molar yield is 98.53%.
Embodiment 7:
The present embodiment technical process as shown in Figure 2.
Be respectively 10m at four volumes
3Oxidation reactor in, per hour add the 45000kg hexanaphthene continuously, make catalyzer with oil-soluble cobalt naphthenate, the HEDP ester is done precipitating inhibitor, contains cobalt ion 0.05ppm in the retaining ring hexane, contains HEDP ester 0.10ppm, under 155 ± 2 ℃ and 0.95 ± 0.03MPa gauge pressure, blowing air carries out oxidation.Per hour obtain containing hexanaphthene 29490kg, pure 605kg, ketone 348kg, sour 166kg, ester 131kg, mistake 550kg, other cyclohexane oxidation mixture of 88 kilograms amounts to 31378kg.The temperature of this oxidation mixture is reduced to 120-130 ℃, the acid Cobaltous diacetate aqueous solution with the 4000kg/h that contains cobalt 1000ppm carries out the heterogeneous catalysis decomposition, decomposing the back material carries out settlement separate, water recycles, during oil phase is undertaken by traditional method with the alkaline aqueous solution that contains 12%NaOH and saponification, isolate buck mutually after, oil phase is delivered to the alkane tower again and is carried out rectifying separation, per hour obtain containing hexalin 895kg, pimelinketone 598kg, other thick pure alcohol/ketone mixtures 1591kg of 98 kilograms, the hexanaphthene Returning oxidation reactor.The molar yield that this technology makes oxidation, decomposition, neutralization, saponification, smart gold-plating operation prepare the hexalin pimelinketone is 85.5%.
Embodiment 8:
The present embodiment technical process is as shown in Figure 3:
Be respectively in the oxidation reactor of 36m3 at four volumes, per hour add the 240000kg hexanaphthene continuously, make catalyzer with oil-soluble cobalt naphthenate, the HEDP ester is done precipitating inhibitor, contain cobalt ion 0.05ppm in the retaining ring hexane, contain HEDP ester 0.1ppm, under 156 ± 2 ℃ and 0.95 ± 0.05MPa gauge pressure, blowing air carries out oxidation.Per hour obtain containing alkane 153155kg, pure 2883kg, ketone 1559kg crosses 2925kg, sour 520kg, ester 308kg, the cyclohexane oxidation mixture that other weight component etc. are 290 kilograms amounts to 161640kg.The temperature of this cyclohexane oxidation mixture is dropped to 120 ℃, with the Cobaltous diacetate acidic aqueous solution 3m that contains cobalt ion 1000ppm
3/ h carries out the heterogeneous catalysis decomposition reaction, and guarantees that the flow of the circulation Cobaltous diacetate aqueous solution is 25 ± 5m
3/ h, guarantee the contact of profit biphase thorough mixing with static mixer, carry out settlement separate after decomposition reaction is finished, during upper oil phase is undertaken by traditional method with the caustic-soda aqueous solution that contains 12%NaOH and saponification, lower floor's water major part recycles, outside the small part discharge system, therefrom reclaim hexanodioic acid and Cobaltous diacetate etc.In and the material after the saponification carry out settlement separately again, remove the alkane tower after the upper oil phase heat exchange, per hour obtain containing pure 4280kg through rectifying, ketone 2870kg, the thick pure alcohol/ketone mixtures of weight component 330kg amounts to 7480kg, the hexanaphthene Returning oxidation reactor.Lower floor's buck phase also major part recycles, and the small part salkali waste is discharged system.The molar yield that the cyclohexane oxidation of this technology, decomposition, neutralization, saponification, rectification working process prepare the hexalin pimelinketone is 86%.
Embodiment 9:
The technical process of present embodiment is as shown in Figure 4:
Be respectively 50m at five volumes
3Oxidation reactor in, per hour add the 211266kg hexanaphthene continuously, add 12 gram HEDP ester passivation reaction walls, under 165 ± 5 ℃ temperature and 1.20 ± 0.05MPa gauge pressure, blowing air carries out non-catalyst oxidation.Per hour obtain containing hexanaphthene 152343kg, pure 1275kg, ketone 538kg crosses 5475kg, sour 247kg, ester 215kg, the cyclohexane oxidation mixture of weight component 42kg amounts to 160135kg.This cyclohexane oxidation mixture is cooled to 113 ℃ through heat exchange, carry out heterogeneous catalysis with the Cobaltous diacetate acidic aqueous solution that contains cobalt ion 1000ppm and decompose, the flow of the Control Circulation Cobaltous diacetate aqueous solution is 30 ± 2m
3/ h per hour adds fresh Cobaltous diacetate aqueous solution 3m
3/ h guarantees profit biphase thorough mixing and contacts with static mixer and agitator, after decomposition reaction is finished, carries out settlement separately, and upper strata tart oil phase cools to 94 ℃, and in being undertaken by traditional method with the alkali aqueous solution that contains NaOH12% and saponification.Lower floor's acidic aqueous solution major part recycles, the about 2.5m of small part
3Outside/h discharge the system, therefrom reclaim hexanodioic acid and Cobaltous diacetate etc.In and saponification after material carry out the sedimentation layering again, remove the alkane rectification tower after the upper oil phase heat exchange, per hour obtain containing pure 4203kg, ketone 2975kg through rectifying, the thick pure alcohol/ketone mixtures of other weight component 120kg amounts to 7298kg, the hexanaphthene Returning oxidation reactor.Lower floor's buck major part mutually recycles, and small part is discharged system with salkali waste.Prepare hexalin with the saponification rectification working process during the cyclohexane oxidation of this technology decomposes, the molar yield of pimelinketone is 88%.
Embodiment 10:
The technical process of present embodiment as shown in Figure 5.
At four diameter 2m, in the tower oxidation reactor of high 11.96m, per hour add the 171341kg hexanaphthene continuously, with trisodium phosphate or HEDP ester passivation reaction wall, under 183 ℃ to 166 ℃ and 1.90 ± 0.05MPa gauge pressure, logical these hexanaphthenes of oxygen-denuded air non-catalyst oxidation that contain oxygen 14% (wt%).Per hour obtain containing hexanaphthene 134038kg, pure 1164kg, ketone 543kg, superoxide 4864kg, ester 409kg, the cyclohexane oxidation mixture 141309kg of neutrals 500kg.This cyclohexane oxidation mixture is reduced to 115 ℃, with the CrO that contains Cr1000ppm
3Acidic aqueous solution carries out heterogeneous catalysis and decomposes, and per hour adds fresh CrO
3Aqueous solution 4643kg prepares the water of this solution, uses from the B1 sour water at the bottom of the D202 oxide compound washing tower, and guarantee profit biphase thorough mixing and contact with static mixer and pipeline reactor, and control CrO
3The circular flow of acidic aqueous solution is 30 ± 2m
3/ h.After decomposition is finished, carry out settlement separate, upper oil phase goes the rectifying of D201 upgrading tower to concentrate, go the D202 washing tower to wash again after concentrating, and then rectifying and dewatering, steam hexanaphthene, pure alcohol/ketone mixtures and heavy constituent, the hexanaphthene Returning oxidation reactor per hour obtains KA oil and 408kg heavy constituent that 6018kg contains alcohol ketone 98.5%.Lower floor's water major part recycles, and outside the small part discharge system, therefrom reclaims hexanodioic acid and chromium acetate etc.The molar yield that this technology cyclohexane oxidation prepares hexalin and pimelinketone is 85%.
Claims (12)
1. the preparation technology of pimelinketone and hexalin, may further comprise the steps (A) in oxidation reactor, 150 ℃-183 ℃ of controlled temperature are under the gauge pressure 0.8-1.95Mpa condition, with the gas cyaniding hexanaphthene of molecule-containing keto, generate the cyclohexane oxidation mixture that contains cyclohexyl hydroperoxide; (B) the cyclohexane oxidation mixture that will contain cyclohexyl hydroperoxide decomposes, and makes it to generate hexalin and pimelinketone; (C) with rectifying separation hexanaphthene, hexalin and pimelinketone product, hexanaphthene Returning oxidation reactor; It is characterized in that decompose in the technology of the cyclohexane oxidation mixture that contains cyclohexyl hydroperoxide, employed catalyzer is the acidic aqueous solution of cobalt salt and/or chromic salts.
2. the preparation technology of hexalin according to claim 1 and pimelinketone is characterized in that, described catalyzer is the aqueous solution of Cobaltous diacetate and/or rose vitriol, Xiao Suangu, chromium acetate, chromic trioxide.
3. according to the preparation technology of claim 1 or described hexalin of claim 2 and pimelinketone, it is characterized in that: in the aqueous solution of described catalyzer, the weight concentration of cobalt and/or chromium is 100-10000ppm.
4. according to the preparation technology of claim 1 or described hexalin of claim 2 and pimelinketone, it is characterized in that in the described aqueous catalyst solution, the weight concentration of cobalt and/or chromium is 500-2000ppm.
5. the preparation technology of hexalin according to claim 1 and pimelinketone is characterized in that catalyzer---the add-on of the aqueous solution of cobalt salt and/or chromic salts is the 1-50% of cyclohexane oxidation volume of mixture flow.
6. according to the preparation technology of claim 1 or described hexalin of claim 5 and pimelinketone, it is characterized in that catalyzer---the add-on of the aqueous solution of cobalt salt and/or chromic salts is the 4-30% of cyclohexane oxidation volume of mixture flow.
7. the preparation technology of hexalin according to claim 1 and pimelinketone is characterized in that, the decomposition temperature that contains the cyclohexane oxidation mixture of cyclohexyl hydroperoxide is 100-160 ℃.
8. according to the preparation technology of claim 1 or described hexalin of claim 7 and pimelinketone, it is characterized in that the decomposition temperature that contains the cyclohexane oxidation mixture of cyclohexyl hydroperoxide is 120-130 ℃.
9. the preparation technology of hexalin according to claim 1 and pimelinketone, it is characterized in that, the decomposition reaction that contains the cyclohexane oxidation mixture of cyclohexyl hydroperoxide can be carried out in counter-current tower, also can carry out in the following current tower or carry out at tubular reactor or in steel basin, the contact reacts time of inorganic phase catalyst cobalt salt and/or aqueous solution of chromium salt and organic phase cyclohexane oxidation mixture is 3 minutes to 180 minutes.
10. according to the preparation technology of claim 1 or described hexalin of claim 9 and pimelinketone, it is characterized in that contact reacts part of aqueous catalyst solution and cyclohexane oxidation mixture is 15 minutes to 40 minutes.
11. the preparation technology of hexalin according to claim 1 and pimelinketone, it is characterized in that, use static mixer during the mixing of inorganic phase catalyst cobalt salt and/or aqueous solution of chromium salt and organic phase cyclohexane oxidation mixture, make aqueous catalyst solution be dispersed into the particle of 1 μ m to 500 μ m, be dispersed in the cyclohexane oxidation mixture.
12. the preparation technology of hexalin according to claim 1 and pimelinketone, it is characterized in that: the reaction mixture after decomposition reaction is finished, enter in the settlement separator and separate, upper organic phase goes to carry out or wash, perhaps alkali cleaning, perhaps directly carry out rectifying, rectifying goes out hexanaphthene and hexalin, pimelinketone; The aqueous solution major part of inorganic phase cobalt salt of lower floor and/or chromic salts is returned decomposition reactor and is done the catalyzer use, outside the small part discharger, therefrom reclaims cobalt salt, chromic salts and hexanodioic acid etc.
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Cited By (7)
| 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 |
| CN102260136A (en) * | 2010-05-26 | 2011-11-30 | 北京石油化工学院 | Method for preparing mixture of cyclohexanone and cyclohexanol by oxidazing cyclohexane liquid phase |
| CN102627541A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
| CN104098433A (en) * | 2014-07-04 | 2014-10-15 | 上海洪鲁化工技术有限公司 | Decomposition method of cyclohexyl hydrogen peroxide |
| CN104177222A (en) * | 2013-05-24 | 2014-12-03 | 中国石油化工股份有限公司 | Method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide |
| CN106542980A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | The method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and Hexalin under slightly acidic condition |
| CN112851483A (en) * | 2021-01-20 | 2021-05-28 | 山东省科学院菏泽分院 | Preparation method of cyclohexanone and cyclohexanol |
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1996
- 1996-12-04 CN CN96118441A patent/CN1184097A/en active Pending
Cited By (9)
| 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 |
| CN102260136A (en) * | 2010-05-26 | 2011-11-30 | 北京石油化工学院 | Method for preparing mixture of cyclohexanone and cyclohexanol by oxidazing cyclohexane liquid phase |
| CN102627541A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
| CN104177222A (en) * | 2013-05-24 | 2014-12-03 | 中国石油化工股份有限公司 | Method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide |
| CN104098433A (en) * | 2014-07-04 | 2014-10-15 | 上海洪鲁化工技术有限公司 | Decomposition method of cyclohexyl hydrogen peroxide |
| CN104098433B (en) * | 2014-07-04 | 2016-03-02 | 上海洪鲁化工技术有限公司 | A kind of decomposition method of cyclohexyl hydroperoxide |
| CN106542980A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | The method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and Hexalin under slightly acidic condition |
| CN112851483A (en) * | 2021-01-20 | 2021-05-28 | 山东省科学院菏泽分院 | Preparation method of cyclohexanone and cyclohexanol |
| CN112851483B (en) * | 2021-01-20 | 2022-08-09 | 山东省科学院菏泽分院 | Preparation method of cyclohexanone and cyclohexanol |
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