CN1152003C - Catalytic decomposition process of cyclohexane oxide liquid - Google Patents
Catalytic decomposition process of cyclohexane oxide liquid Download PDFInfo
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- CN1152003C CN1152003C CNB011184388A CN01118438A CN1152003C CN 1152003 C CN1152003 C CN 1152003C CN B011184388 A CNB011184388 A CN B011184388A CN 01118438 A CN01118438 A CN 01118438A CN 1152003 C CN1152003 C CN 1152003C
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Abstract
The present invention relates to a catalytic decomposition process of a cyclohexane oxide liquid, which comprises: 70 to 1000 ml of cyclohexane oxide liquid and 1g of CAPO-5 Cr-P-Al molecular sieve are mixed and react at the temperature of 50 to 80 DEG C and under normal pressure or at 80 to 150 DEG C and under the pressure of 0.1 to 0.4MPa, wherein the CAPO-5 Cr-P-Al molecular sieve is synthesized by using ethyl chromate or tertiary butyl chromate as a chromium source. The process has no environmental pollution, and compared with the prior art, the yield of the process is increased by 2 to 10%.
Description
The invention relates to the catalytic decomposing method of cyclohexane oxide solution, further say so about with the molecular sieve being the method that the catalytic decomposition of the cyclohexane oxide solution of catalyzer is produced hexalin and pimelinketone.
At present, cyclohexane oxidation is produced the production technique widespread use in the world of hexalin, pimelinketone, and the whole world has 3,500,000 tons of hexalin, pimelinketone to adopt hexanaphthene liquid phase air oxidation technology to make every year approximately according to statistics.
In the reaction mechanism of cyclohexane oxidation, hexanaphthene at first is oxidized to cyclohexyl hydroperoxide, and cyclohexyl hydroperoxide continues to be decomposed into pimelinketone and hexalin.And from the fifties to the early sixties, it is believed that have only hexalin, useful products that pimelinketone is only cyclohexane oxidation, understanding to cyclohexyl hydroperoxide is also not enough, fear that superoxide easily sets off an explosion, therefore reduce the content of superoxide in the oxidation liquid as far as possible, make it after generating, immediately under aerobic environment, in stills for air blowing, resolve into hexalin and pimelinketone, but the processing method of high basicity and weak mass transfer makes this peroxide breakdown become the yield of hexalin, pimelinketone low.
Arrived after the middle nineteen sixties, people have had raising to the understanding of cyclohexyl hydroperoxide.In order to overcome the slagging scorification problem that high catalyst concentration causes, the catalyst cobalt ionic concn is reduced to below the 1ppm, therefore cyclohexyl hydroperoxide content also be increased to more than 1% in the oxidation liquid, and developed than the alkaline much lower yellow soda ash neutralization of sodium hydroxide, decomposition technique, use static mixer to carry out mixing of alkali lye and oxidation liquid, improved mass transfer effect greatly, the decomposition yield of cyclohexyl hydroperoxide under alkaline condition improved.
The low temperature non-catalyst oxidation and the low temperature heterogeneous catalysis decomposition method (being called DSM/HPO technology) of the exploitation of Holland DSM N. V. further improve cyclohexane oxidation, decomposition course total recovery, and the design yield is 84%.In this method, the transformation efficiency of cyclohexane oxidation remains on 3-4%, and the oxidation liquid of gained contacts with the sodium hydroxide cobalt acetate solution again, reacts 24 minutes under 3atm, 85 ℃ of conditions, and cyclohexyl hydroperoxide wherein resolves into the mixture of pimelinketone and hexalin.The deficiency of this method is: (1) because under alkaline condition, ketone, alcohol can further deep oxidation be acid, carry out condensation reaction with ketone, alcohol again, so the yield of pimelinketone and hexalin is not high, actual recovery is only about 80%; (2) this operational path complexity, intermediate steps are many, and reagent has corrodibility, and three wastes discharge amount is big, and environmental pollution is serious.
USP 4759919 disclosed CAPO-5 Cr-P-Al molecular sieves have the crystalline structure of AFI.Reported that with the CAPO-5 molecular sieve be catalyzer in Applied Catalysis A:General 108 (1994) L1-L6, cyclohexyl hydroperoxide is decomposed into the reaction result of pimelinketone and hexalin.This reaction is that cyclohexyl hydroperoxide, hexanaphthene and CAPO-5 molecular sieve were reacted 5 hours at 70 ℃, and the transformation efficiency of cyclohexyl hydroperoxide is 87%, and the selectivity of pimelinketone and hexalin is respectively 86% and 13%.But the raw material of this reaction is homemade cyclohexyl hydroperoxide, rather than the Industrial products of cyclohexane oxide solution.
Up to now, yet there are no the report that decomposes industrial cyclohexane oxide solution generation pimelinketone and hexalin with the CAPO-5 molecular sieve catalytic.
The objective of the invention is on the basis of existing technology, providing a kind of is the reaction object with the industrial raw material, the catalytic decomposing method of the cyclohexane oxide solution of non-environmental-pollution.
One of method provided by the invention be with the CAPO-5 Cr-P-Al molecular sieve of the cyclohexane oxide solution of ml volumes and gram weight according to 70-1000: 1, preferred 100-800: after 1 the mixed, reaction is 0.1-2 hour under 50-80 ℃, normal pressure.
Two of method provided by the invention be with said mixture at 80-150 ℃, preferred 100-120 ℃, keep reaction 0.1-2 hour down of 0.1-0.4MPa, preferred 0.12-0.35MPa pressure.
Said in the present invention cyclohexane oxide solution is a mixture, generally contains the heavy % of hexanaphthene 95-96, the heavy % of cyclohexyl hydroperoxide 3-4, and the hexalin of surplus, pimelinketone, acid and ester.This cyclohexane oxide solution be with hexanaphthene under the industrial condition of catalyst-free, 160-165 ℃, 1.2-1.3MPa, the conversion rate of oxidation of control 3-4% obtains, the primary product of cyclohexane oxidation is a cyclohexyl hydroperoxide.Except above-mentioned cyclohexane oxide solution, the cyclohexane oxide solution of other composition also is applicable to the present invention, the cyclohexane oxide solution of the above-mentioned composition enriched product after methods such as distillation are partly separated wherein hexanaphthene component also be can be used as stock liquid, be suitable for the present invention.
The CAPO-5 Cr-P-Al molecular sieve that is adopted in the inventive method, its crystal powder structural code is AFI, has Zeolite 16:323-802, the feature of the X-ray diffraction spectrogram of 1,996 353 disclosed AFI crystalline structure molecular sieves.
In the catalytic decomposing method of cyclohexane oxide solution provided by the invention, used CAPO-5 Cr-P-Al molecular sieve, be that chromic acid ethyl ester or chromic acid tert-butyl are mixed with the phosphorus source in the adding aluminium source, back, mix, aging 1-10 hour, add organic formwork agent and water, obtain mole and consist of (0.005-0.1) Cr
2O
3: (0.8-1.2) Al
2O
3: P
2O
5: (1-3) template: (10-100) H
2The mixed solution of O, with mixed solution in closed reactor 150-180 ℃ after crystallization 1-10 days, with ordinary method filter, washing, dry, roasting obtain.
In the above-mentioned method for preparing the CAPO-5 Cr-P-Al molecular sieve, said chromic acid ethyl ester, its molecular formula is Cr (OCH
2CH
3)
3, can adopt following process synthetic: according to stoichiometry, sodium Metal 99.5 to be contacted the generation sodium ethylate with ethanol, the sodium ethylate that generates is generated the chromic acid ethyl ester with the chromic salts reaction again.
In the above-mentioned method for preparing the CAPO-5 Cr-P-Al molecular sieve, said chromic acid tert-butyl, its molecular formula is Cr (OCCH
3CH
3CH
3)
3, can adopt following process synthetic: according to stoichiometry, sodium Metal 99.5 to be contacted the generation sodium tert-butoxide with the trimethyl carbinol, the sodium tert-butoxide that generates is generated chromic acid tert-butyl with the chromic salts reaction again.
When synthetic chromic acid ethyl ester or chromic acid tert-butyl, wherein said chromic salts is selected from one of chromium chloride, chromium nitrate or chromium acetate.
In the above-mentioned method for preparing the CAPO-5 Cr-P-Al molecular sieve, said aluminium source is selected from one of aluminum isopropoxide, boehmite, pseudo-boehmite, aluminium colloidal sol, aluminum phosphate, gibbsite, sodium aluminate or aluminum chloride, wherein preferred boehmite, pseudo-boehmite or aluminium colloidal sol.Said aluminium source generally can be dissolved in the nitric acid in use to be accelerated into the glue process.
Said phosphorus source is selected from phosphoric acid, triethyl phosphoric acid or metaphosphate, wherein preferred ortho-phosphoric acid.
Said organic formwork agent is selected from one of di-n-propylamine, Tri-n-Propylamine or tetraethyl ammonium hydroxide or their mixture.
The catalytic decomposing method of cyclohexane oxide solution provided by the invention has following advantage with respect to prior art:
1. the acid and the amount of ester can be kept the previous level of oxidation liquid in the oxidation liquid degradation production, do not increase acid and ester newly, and yield is than 2-10 percentage point of prior art raising.
2. be in non-alkaline environment, to carry out owing to reacting, thereby avoided adding the problem of environmental pollution that sodium hydroxide brings.
Fig. 1 is Zeolite 16:323-802,1,996 353 disclosed Standard X-Ray diffraction spectrograms with AFI crystalline structure molecular sieve.
Below will the present invention is further illustrated with example, but content of the present invention is not subjected to the restriction of these examples.
The preparation process of example 1-7 explanation CAPO-5 Cr-P-Al molecular sieve.
In example, the X-ray diffraction analysis is carried out on the D5005D type x-ray diffractometer of German SIEMENS company, and condition is 40KV, 40mA, K alpha-ray Cu target.
Example 1
The preparation process of this example explanation chromic acid ethyl ester.
Restrain sodium Metal 99.5s with 23 and join several times in 200 ethanol that restrain, generate sodium ethylate 69 grams, restrain contact reactss, generate the chromic acid ethyl esters of 58.3 grams with the sodium ethylate of generation and through the chromium chloride 52.8 of 100 ℃ of dryings after 4 hours.
Example 2
The preparation process of this example explanation chromic acid tert-butyl.
Restrain sodium Metal 99.5s with 23 and join several times in 250 ethanol that restrain, generate sodium ethylate 96 grams, restrain contact reactss, generate the chromic acid tert-butyls of 271 grams with the sodium tert-butoxide of generation and through the chromium chloride 52.8 of 100 ℃ of dryings after 4 hours.
Example 3
76 grams, 56% boehmite is dissolved in 350 gram 1N HNO
3In the solution, pour 104 grams, 85% phosphoric acid into, add 8.4 gram chromic acid ethyl esters again, mix and stirred 4 hours, drip 98 gram Tri-n-Propylamine (Pr
3N), vigorous stirring obtains forming: 0.05Cr
2O
3: P
2O
5: 0.93Al
2O
3: 1.5Pr
3N:50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filters, washing, 120 ℃ of dryings 2 hours, get white solid,, get sieve sample Z1 in 550 ℃ of roastings 10 hours, the X-ray diffraction wave spectrum of this sample has the feature of Fig. 1, illustrates that this molecular sieve has the crystalline structure of AFI.
Example 4
43 grams, 66% pseudo-boehmite is dissolved in 174 gram 1N HNO
3In the solution, pour in 69 grams, 85% phosphoric acid, add 2.8 gram chromic acid ethyl esters again, also stirred 4 hours the mixing back, and the 90 gram 24.0%TEAOH aqueous solution are added drop-wise in the said mixture.And then drip 60 gram di-n-propylamine (Pr
2NH), vigorous stirring obtains forming: 0.025Cr
2O
3: P
2O
5: 0.93Al
2O
3: 2.0Pr
2NH:0.50TEAOH:50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filter, washing, 110 ℃ of dryings 4 hours, white solid, in 550 ℃ of roastings 10 hours, sieve sample Z2.This sample has X-ray diffraction wave spectrum feature shown in Figure 1.
Example 5
170 gram 25% aluminium colloidal sols (Haiyang Chemical Plant, Qingdao's product) and 4.22 gram chromic acid ethyl esters are poured in 104 grams, 85% phosphoric acid, add water 58 gram, mix and stirred 4 hours, again the 270 gram 24.0%TEAOH aqueous solution are added drop-wise in the said mixture, vigorous stirring obtains forming 0.025Cr
2O
3: P
2O
5: 0.93Al
2O
3: 1.0TEAOH:50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filter, washing, 120 ℃ of dryings 3 hours, white solid, in 550 ℃ of roastings 10 hours, sieve sample Z3.This sample has X-ray diffraction wave spectrum feature shown in Figure 1.
Example 6
76 grams, 56% boehmite is dissolved in 350 gram 1N HNO
3In the solution, pour 104 grams, 85% phosphoric acid into, add 12.2 gram chromic acid tert-butyls again, mix and stirred 4 hours, drip 98 gram Tri-n-Propylamine (Pr
3N), vigorous stirring obtains consisting of 0.05Cr
2O
3: P
2O
5: 0.93Al
2O
3: 1.5Pr
3N:50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filters, washing, 120 ℃ of dryings 3 hours, get white solid,, get sieve sample Z4 in 550C roasting 10 hours, the X-ray diffraction wave spectrum of this sample has the feature of Fig. 1, illustrates that this molecular sieve has the crystalline structure of AFI.
Example 7
76 grams, 56% boehmite is dissolved in 350 gram 1N HNO
3In the solution, 8.4 gram chromic acid ethyl esters are poured in 104 grams, 85% phosphoric acid, mix and stir 4 hours, drip 65 gram Tri-n-Propylamine (Pr
3N), vigorous stirring obtains forming: 0.05Cr
2O
3: P
2O
5: 0.9Al
2O
3: 1.0Pr
3N:50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filter, washing, 100 ℃ of dryings 4 hours, white solid, in 550 ℃ of roastings 10 hours, sieve sample Z5, this sample has X-ray diffraction wave spectrum feature shown in Figure 1.
Following example illustrates the catalytic decomposing method of cyclohexane oxide solution provided by the invention.
Cyclohexane oxide solution in the example consists of: hexanaphthene 95.1029%, hexalin 0.7975%, pimelinketone 0.3366%, cyclohexyl hydroperoxide 3.4243%, acid 0.1547%, ester 0.1344%.
In following example, the transformation efficiency iodometric determination of cyclohexyl hydroperoxide: getting a certain amount of reaction product, to be dissolved in volume ratio be in chloroform/acetic acid of 1: 2, adds the saturated solution of potassiumiodide, and lucifuge left standstill 20 minutes, add de-salted water then, use the Sulfothiorine titration.
The analysis of pimelinketone and hexalin: in the reaction product, add after the excessive triphenyl phosphine that is dissolved in the acetone removes remaining cyclohexyl hydroperoxide, use gas chromatographic analysis, GLC CP WAX 52 CB chromatographic columns.
The conventional chemical titration of acid and ester.
During cyclohexylhydroperoxconversion conversion rate and alcohol, ketone, acid, ester optionally calculated in the oxidation liquid, the acid in the oxidation liquid was in hexanodioic acid (molecular weight 146), and ester is in hexanodioic acid hexamethylene diester (molecular weight 310).
Decompose yield %=(pimelinketone selectivity+hexalin selectivity) * cyclohexylhydroperoxconversion conversion rate * 100
In being decomposed into the reaction process of hexalin and pimelinketone, cyclohexyl hydroperoxide produced atomic oxygen, atomic oxygen continues to generate hexalin and pimelinketone with hexanaphthene generation oxidizing reaction, and the selectivity that causes pimelinketone that whole decomposition reaction calculates based on superoxide, alcohol is greater than 100%.
Example 8-13 illustrates the catalytic decomposing method of oxidation liquid provided by the invention under normal pressure, and example 14-18 illustrates the reaction result under the band press strip spare provided by the invention.
Example 8-13
In having three mouthfuls of glass reactors of reflux, add 36 milliliters of above-mentioned cyclohexane oxide solutions and CAPO-5 molecular sieve, under different reaction conditionss, carry out decomposition reaction, the reaction result of gained sees Table 1.
Example 14-18
Be reflected at 1000 milliliters polytetrafluoroethyllining lining pressure and hold in the bullet and carry out, add, under different reaction conditionss, carry out decomposition reaction with example 5 used 720 milliliters of cyclohexane oxide solutions and molecular sieve.Reaction conditions and gained reaction result are listed in the table 2.
Table 1
| Example number | Molecular sieve numbering and consumption (gram) | Reaction conditions | Acid mmol/g | Ester mmol/g | Pimelinketone selectivity % | Hexalin selectivity % | Cyclohexylhydroperoxconversion conversion rate % | Yield % |
| 8 | Z1，0.1 | 0.5 hours 80 ℃ | 0.061 | 0.023 | 75.1 | 33.5 | 82.5 | 89.6 |
| 9 | Z5，0.1 | 0.5 hours 80 ℃ | 0.048 | 0.019 | 70.3 | 37.4 | 78.3 | 84.3 |
| 10 | Z2，0.1 | 0.5 hours 80 ℃ | 0.044 | 0.017 | 75.1 | 35.2 | 90.5 | 99.8 |
| 11 | Z4，0.1 | 1 hour 80 ℃ | 0.051 | 0.014 | 74.6 | 37.1 | 90.4 | 100.9 |
| 12 | Z4，0.25 | 2 hours 80 ℃ | 0.057 | 0.014 | 74.0 | 36.6 | 92.6 | 102.4 |
| 13 | Z4，0.05 | 4 hours 60 ℃ | 0.057 | 0.014 | 74.7 | 37.6 | 86.1 | 96.7 |
Table 2
| Example number | Molecular sieve numbering and consumption (gram) | Reaction conditions | Acid mmol/g | Ester mmol/g | Pimelinketone selectivity % | Hexalin selectivity % | Cyclohexylhydroperoxconversion conversion rate % | Yield % |
| 14 | Z1，1.0 | 0.5 hour, 100 ℃, 0.12MPa | 0.043 | 0.018 | 70.3 | 37.4 | 94.8 | 102.1 |
| 15 | Z2，6.0 | 4 hours, 120 ℃, 0.36M Pa | 0.062 | 0.018 | 74.6 | 34.1 | 98.6 | 107.2 |
| 16 | Z3，2.0 | 1 hour, 120 ℃, 0.2MPa | 0.043 | 0.017 | 74.0 | 36.6 | 98.0 | 108.4 |
| 17 | Z4，3.0 | 1 hour, 120 ℃, 0.3MPa | 0.055 | 0.015 | 73.1 | 32.5 | 96.6 | 102.0 |
| 18 | Z4，3.0 | 0.5 hour, 120 ℃, 0.3MPa | 0.040 | 0.012 | 71.8 | 36.7 | 94.6 | 102.6 |
Claims (10)
1, a kind of catalytic decomposing method of cyclohexane oxide solution, it is characterized in that the CAPO-5 Cr-P-Al molecular sieve of the cyclohexane oxide solution of ml volumes and gram weight according to 70-1000: after 1 the mixed, reaction is 0.1-2 hour under temperature 50-80 ℃, normal pressure, CAPO-5 Cr-P-Al molecular sieve wherein is chromic acid ethyl ester or chromic acid tert-butyl to be dissolved in deionized water mix with phosphoric acid, mix with the hydrating solution in aluminium source again and wore out 1-10 hour, add organic formwork agent, mix, the mole that obtains is consisted of 0.005-0.1Cr
2O
3: 0.8-1.2Al
2O
3: 1-3 template: P
2O
5: 10-100H
2The mixing solutions of O, in closed reactor 150-180 ℃ after crystallization 1-10 days, filtration, washing, drying and roasting obtain.
2,, it is characterized in that the CAPO-5 Cr-P-Al molecular sieve of the cyclohexane oxide solution of ml volumes and gram weight with 100-800: 1 mixed according to the method for claim 1.
3,, it is characterized in that described oxidation liquid contains the hexanaphthene of the heavy % of 95-96, the cyclohexyl hydroperoxide of the heavy % of 3-4 and hexalin, pimelinketone, acid and the ester of surplus according to the method for claim 1 or 2.
4, in accordance with the method for claim 1, it is characterized in that described aluminium source is selected from one of boehmite, pseudo-boehmite or aluminium colloidal sol.
5, in accordance with the method for claim 1, it is characterized in that described organic formwork agent is selected from one of di-n-propylamine, Tri-n-Propylamine or tetraethyl ammonium hydroxide or its mixture.
6, a kind of catalytic decomposing method of cyclohexane oxide solution, it is characterized in that the CAPO-5 Cr-P-Al molecular sieve of the cyclohexane oxide solution of ml volumes and gram weight according to 70-1000: after 1 the mixed, 80-150 ℃, keep under the 0.1-0.4MPa pressure reaction 0.1-2 hour, CAPO-5 Cr-P-Al molecular sieve wherein is chromic acid ethyl ester or chromic acid tert-butyl to be dissolved in deionized water mix with phosphoric acid, mix with the hydrating solution in aluminium source again and wore out 1-10 hour, add organic formwork agent, mix, the mole that obtains is consisted of 0.005-0.1Cr
2O
3: 0.8-1.2Al
2O
3: 1-3 template: P
2O
5: 10-100H
2The mixing solutions of O, in closed reactor 150-180 ℃ after crystallization 1-10 days, filtration, washing, drying and roasting obtain.
7,, it is characterized in that the CAPO-5 Cr-P-Al molecular sieve of the cyclohexane oxide solution of ml volumes and gram weight with 100-800: 1 mixed according to the method for claim 6.
8,, it is characterized in that described oxidation liquid contains the hexanaphthene of the heavy % of 95-96, the cyclohexyl hydroperoxide of the heavy % of 3-4 and hexalin, pimelinketone, acid and the ester of surplus according to the method for claim 6 or 7.
9, in accordance with the method for claim 6, it is characterized in that described aluminium source is selected from one of boehmite, pseudo-boehmite or aluminium colloidal sol.
10, in accordance with the method for claim 6, it is characterized in that described organic formwork agent is selected from one of di-n-propylamine, Tri-n-Propylamine or tetraethyl ammonium hydroxide or its mixture.
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|---|---|---|---|
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|---|---|---|---|
| CNB011184388A CN1152003C (en) | 2001-05-30 | 2001-05-30 | Catalytic decomposition process of cyclohexane oxide liquid |
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| CN110437037A (en) * | 2018-05-04 | 2019-11-12 | 江西和德瑞新材料有限公司 | A kind of method of cyclohexane oxide solution processing |
| CN110437048A (en) * | 2018-05-04 | 2019-11-12 | 江西和德瑞新材料有限公司 | A kind of method of cyclohexane oxide solution processing |
| CN110437032A (en) * | 2018-05-04 | 2019-11-12 | 江西和德瑞新材料有限公司 | A kind of method of cyclohexane oxide solution processing |
| CN112239212B (en) * | 2019-07-19 | 2022-06-07 | 浙江恒逸石化研究院有限公司 | Silicon molecular sieve with MFI topological structure and preparation method and application thereof |
| CN112961048B (en) * | 2021-02-08 | 2022-10-18 | 中国石油大学(华东) | Technological method for co-producing K.A. oil and adipic acid by one-step method |
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