CN1300074C - Catalytic decomposition cyclohexane hydrogen peroxide reaction system - Google Patents
Catalytic decomposition cyclohexane hydrogen peroxide reaction system Download PDFInfo
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- CN1300074C CN1300074C CNB2004100546093A CN200410054609A CN1300074C CN 1300074 C CN1300074 C CN 1300074C CN B2004100546093 A CNB2004100546093 A CN B2004100546093A CN 200410054609 A CN200410054609 A CN 200410054609A CN 1300074 C CN1300074 C CN 1300074C
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 59
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims abstract description 8
- PWTGXYFKQRZBEV-UHFFFAOYSA-N cyclohexane;hydrogen peroxide Chemical compound OO.C1CCCCC1 PWTGXYFKQRZBEV-UHFFFAOYSA-N 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 26
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000010931 gold Substances 0.000 claims abstract description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011949 solid catalyst Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 229910002796 Si–Al Inorganic materials 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LQYKMFJYAYZJGE-UHFFFAOYSA-N cyclohexane;hydroperoxycyclohexane Chemical compound C1CCCCC1.OOC1CCCCC1 LQYKMFJYAYZJGE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- 238000000207 volumetry Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种催化分解环己烷过氧化氢反应体系。所使用的催化剂包括负载型催化剂如钌/碳、金/氧化铝；含铬MCM41；以及酸性β分子筛等。分解反应在含有极性溶剂如乙醇，水等介质存在下进行。与现有催化分解环己烷过氧化氢反应体系相比，本发明的突出特点是由于使用了极性溶剂而避免了所使用的催化剂失活，使催化剂可以长期使用。The invention relates to a reaction system for catalytically decomposing cyclohexane hydroperoxide. The catalysts used include supported catalysts such as ruthenium/carbon, gold/alumina; chromium-containing MCM41; and acidic β molecular sieves, etc. The decomposition reaction is carried out in the presence of a medium containing polar solvents such as ethanol and water. Compared with the existing catalytic decomposition reaction system of cyclohexane hydroperoxide, the outstanding feature of the present invention is that the catalyst deactivation is avoided due to the use of a polar solvent, so that the catalyst can be used for a long time.
Description
Technical field
The present invention relates to a kind of catalytic decomposition of cyclohexane hydroperoxide reaction system.
Background technology
The cyclohexyl hydroperoxide decomposition reaction is that cyclohexane oxidation prepares one of important step in hexalin and the whole technological process of pimelinketone.Its decomposition reaction can be expressed as follows with chemical equation:
Existing commercial run is to use a large amount of sodium hydroxide lyes that contains cobalt ion to decompose cyclohexyl hydroperoxide.There is the cost height in this method, generates to contain the organism alkaline waste water in a large number and contaminate environment, and shortcoming such as etching apparatus and yield be low.Environment for use close friend's solid catalyst replaces traditional liquid caustic soda and decomposes cyclohexyl hydroperoxide, is one of target of laying siege to of scientific and technological circle and business circles in recent years.
Germany BASF (BASF) company has used molecular sieve carried transition metal (as cobalt, copper and iron), precious metal (as ruthenium) catalyst decomposes cyclohexyl hydroperoxide in patent WO 200024698.Decomposition reaction is carried out in the cyclohexane medium system.
Dupont (Du Pond) company has proposed to use the Au/Al that modifies through organosilicon in patent WO 200216296
2O
3Decompose cyclohexyl hydroperoxide.Decomposition reaction is carried out in the cyclohexane medium system.
France Luo Diya (Rhodia) company working load type ruthenium catalyst in patent WO 03/037839 decomposes cyclohexyl hydroperoxide.Employed carrier comprises gac, aluminum oxide, zirconium white and magnesium oxide etc.Employed solvent system comprises hexanaphthene, pentamethylene, benzene and toluene etc.
One of shortcoming of using above-mentioned organic solvent reaction system is the easy inactivation of catalyzer.
One of working load shaped metal catalyzer decomposes cyclohexyl hydroperoxide in alkane or aromatic hydrocarbon medium problem is, because in the presence of superoxide, side reactions such as polymerization can take place in pimelinketone and other unsaturated organic impurity, make poisoning of catalyst and can't life-time service.
Comprehensive existing document also not have about making water, the ethanol isopolarity solvent report as the catalytic decomposition of cyclohexane hydroperoxide reaction system.Do not see relevant catalyzer repeated use effect report yet.
Summary of the invention
Main purpose of the present invention is to utilize the reaction system of polar solvent and hexanaphthene coexistence, uses solid catalyst to decompose cyclohexyl hydroperoxide, has avoided catalyst deactivation, urges the purpose that the ring agent can life-time service thereby reach to make.
For achieving the above object, technical scheme of the present invention is to contain the cyclohexane solution of cyclohexyl hydroperoxide, under the liquid-phase condition of water or the existence of Fatty Alcohol(C12-C14 and C12-C18) isopolarity solvent, make cyclohexyl hydroperoxide catalytic decomposition wherein, obtain the reaction system of hexalin and pimelinketone.Employed catalyzer comprises the load type metal catalyst that is loaded with precious metals such as ruthenium, contains the typical catalyst that the MCM-41 type molecular sieve of transition metal such as chromium and Hydrogen beta-molecular sieve etc. have the peroxide breakdown ability in the skeleton.
Of the present invention main form, prolong organo-peroxide decomposition catalyst work-ing life by changing reaction medium.Make under the condition of water, another benefit of this reaction system is to be convenient to separating and recovery such as byproduct organic acid of catalyzer and product.
According to the present invention, reaction substrate is the cyclohexyl hydroperoxide cyclohexane solution.This solution is generally obtained by cyclohexane oxidation (or oxidation liquid is through distillation).In this solution contained cyclohexyl hydroperoxide amount by weight percentage, generally between 0.5-50%.Simultaneously can contain other compositions such as a certain amount of hexalin, pimelinketone and organic acid in the reaction solution.
According to the present invention, employed cyclohexyl hydroperoxide cyclohexane solution can through further purifying treatment or without any processing directly as cartalytic decomposition effect liquid.
According to the present invention, employed polar solvent can be for as organic solvent or water such as methyl alcohol, ethanol.The addition of solvent can be the 0.1-100% of cyclohexyl hydroperoxide cyclohexane solution weight.If be organic alcohol solvent, consider cost and be convenient to and reclaim that consumption should be few as far as possible under the prerequisite that guarantees catalyst activity, be preferably the 0.1-5% of superoxide organic liquor.If be water, then for the ease of separating catalyst and help byproduct such as organic acid reclaims, its usage quantity is preferably the 10-50% of superoxide organic liquor.Reaction system is a two-phase when static when making water, and wherein solid catalyst is present in aqueous phase, and inclining organic phase, stays the water that contains solid catalyst and reuses.If when being solvent, reuse with filter method Separation and Recovery solid catalyst with organic alcohol.
According to the present invention, employed catalyzer can be for by the MCM-41 and the beta molecular sieve that contain transition metal in the loaded catalyst of existing known references method preparation or the technical grade supported solid catalyst backbone.
According to the present invention, the metal active constituent of loaded catalyst comprises transition metal such as cobalt, iron etc.; And precious metal such as ruthenium, gold etc.The supported catalyst agent carrier comprises general carrier such as aluminum oxide, silicon oxide, zirconium white, gac and molecular sieve.The method for preparing catalyst of loading type can be the common pickling process or the precipitator method.Metal active constituent content is counted 0.1-10% with total catalyst weight.Be preferably between the 1-5%.
According to the present invention, employed molecular sieve type catalyst comprises the general commercial molecular sieves such as MCM-41 type molecular sieve that contain components such as cobalt, chromium in Hydrogen beta-molecular sieve and the skeleton, and the content of components such as cobalt, chromium is counted 0.1-2% with total catalyst weight.
According to the present invention, the add-on of catalyzer is counted 0.5-5% by the reactant solution gross weight.
According to the present invention, to cross to decompose in the airtight metallic reactors that is reflected at the band stirring and carry out, stirring velocity can be 50-1500 rev/min, is preferably common industrial stirring velocity 50-300 rev/min.
According to the present invention, cross decomposition reaction and can between 60-170 ℃, carry out, but be preferably between 80-130 ℃, cooling after constant temperature 10-60 minute.Reaction pressure can be 0.1-0.6MPa according to temperature of reaction.
Embodiment
Following example will specify specific implementation method of the present invention.
Embodiment one:
Each 0.1 gram that adds contains the cyclohexane solution that the cyclohexyl hydroperoxide amount is 94.4mmol/Kg by 5%Ru/C catalyzer and 10 grams that document WO 03/037839 method prepares in 50 milliliters of stainless steel cauldrons that a charged magnetic stirs, again to wherein adding a certain amount of water.Reactor is earlier with behind the nitrogen replacement, seals while stirring heat temperature raising to 85 ℃ again, continues isothermal reaction and lower the temperature after 20 minutes, the taking-up resultant of reaction.With cyclohexyl hydroperoxide content before and after the iodo-Sulfothiorine oxidation reduction process volumetry analytical reaction, with hexalin and pimelinketone amount in reaction solution and the Generation Liquid before and after the vapour phase chromatogram marker method analytical reaction.
Cyclohexyl hydroperoxide (CNNP) transformation efficiency calculates as follows:
Cyclohexyl hydroperoxide transformation efficiency=(CNNP concentration (mmol/Kg) in the initial feed)-(CNNP concentration (mmol/Kg) in the product)/(CNNP concentration (mmol/Kg) in the initial feed)
Catalyzer repeated use process is: after reaction finishes, with the organic liquid phase in the reaction system incline or leach after stay the water that contains solid catalyst, add the reaction solution that contains cyclohexyl hydroperoxide again, be warming up to assigned temperature under and react.Comparison example wherein is for except that adding the water, the result who obtains under all identical reaction conditions of all the other operation stepss.Test-results is shown in Table 1, and wherein last hurdle is a comparative test result in the table 1.
Table 1 uses the 5%Ru/C catalyzer that CNNP decomposition contrast under the anhydrous existence condition is arranged again
| Test number | First set reaction amount of water (Wt%) | The catalyst recirculation number of times | CNNP content (mmol/Kg) before the reaction | Reaction back CNNP content (mmol/Kg) | CNNP transformation efficiency (%) |
| 1 | 10 | 0 | 94.4 | 0.00 | 100 |
| 2 | 3 | 2.50 | 97.4 | ||
| 3 | 20 | 6.70 | 92.9 | ||
| 4 | 30 | 0 | 94.4 | 0.00 | 100 |
| 5 | 3 | 0.00 | 100 | ||
| 6 | 50 | 5.30 | 94.4 | ||
| 7 | 50 | 0 | 94.4 | 0.00 | 100 |
| 8 | 3 | 0.00 | 100 | ||
| 9 | 110 | 1.30 | 98.6 | ||
| 10 | 0 | 0 | 94.4 | 0.00 | 100 |
| 11 | 3 | 26.70 | 71.7 | ||
| 12 | 4 | 47.80 | 49.3 |
Embodiment two:
Use 0.1 gram silica alumina ratio (SiO
2/ Al
2O
3) be that 25 industrial Hydrogen β Si-Al molecular sieve replaces the 5%Ru/C catalyzer, the reaction times is that 30 minutes other conditions are all with embodiment one.Reaction result sees Table 2.
Table 2 has β type Si-Al molecular sieve catalysis CNNP decomposition contrast under the anhydrous existence condition
| Test number | First set reaction amount of water (Wt%) | The catalyst recirculation number of times | CNNP content (mmol/Kg) before the reaction | Reaction back CNNP content (mmol/Kg) | CNNP transformation efficiency (%) |
| 1 | 10 | 0 | 94.4 | 0.00 | 100 |
| 2 | 3 | 2.10 | 97.8 | ||
| 3 | 60 | 5.80 | 93.8 | ||
| 4 | 30 | 0 | 94.4 | 0.00 | 100 |
| 5 | 3 | 1.40 | 98.5 | ||
| 6 | 35 | 3.50 | 96.3 | ||
| 7 | 50 | 0 | 94.4 | 1.30 | 98.6 |
| 8 | 3 | 9.30 | 90.1 | ||
| 9 | 50 | 12.70 | 86.5 | ||
| 10 | 0 | 0 | 94.4 | 0 | 100 |
| 11 | 3 | 42.70 | 54.7 | ||
| 12 | 4 | 50.70 | 46.3 |
Embodiment three:
Use the MCM-41 type molecular sieve catalyst that contains Cr1.5% in the skeleton, the reaction times is 30 minutes, and temperature of reaction is 125 ℃, and other condition is all with embodiment one.Reaction result sees Table 3.
Table 3 has the MCM-41 type molecular sieve catalytic CNNP of Cr1.5% under the anhydrous existence condition to decompose contrast
| Test number | First set reaction amount of water (Wt%) | The catalyst recirculation number of times | CNNP content (mmol/Kg) before the reaction | Reaction back CNNP content (mmol/Kg) | CNNP transformation efficiency (%) |
| 1 | 50 | 0 | 123.5 | 0.00 | 100 |
| 2 | 60 | 2.00 | 98.3 | ||
| 3 | 0 | 0 | 123.5 | 0.00 | 100 |
| 4 | 3 | 76.00 | 38.5 | ||
| 5 | 4 | 83.20 | 32.6 |
Embodiment four:
Use 0.1 gram silica alumina ratio (SiO
2/ Al
2O
3) be that 25 industrial Hydrogen β Si-Al molecular sieve replaces the 5%Ru/C catalyzer, add solvent and change ethanol into by water, leach reaction solution after the reaction, stay solid catalyst charging reaction again.Other condition is all with embodiment one.Reaction result sees Table 4.
Table 4 has β type Si-Al molecular sieve catalysis CNNP decomposition contrast under the ethanol existence condition
| Test number | First set reaction adds amount of alcohol (Wt%) | The catalyst recirculation number of times | CNNP content (mmol/Kg) before the reaction | Reaction back CNNP content (mmol/Kg) | CNNP transformation efficiency (%) |
| 1 | 2 | 0 | 94.4 | 6.7 | 92.9 |
| 2 | 3 | 9.5 | 89.9 | ||
| 3 | 30 | 10.2 | 89.2 | ||
| 4 | 8 | 0 | 94.4 | 1.5 | 98.4 |
| 5 | 3 | 8.0 | 91.5 | ||
| 6 | 35 | 9.3 | 90.1 | ||
| 7 | 40 | 0 | 94.4 | 17.8 | 81.1 |
| 8 | 3 | 18.7 | 80.2 | ||
| 9 | 45 | 15.6 | 83.5 |
| 10 | 0 | 0 | 94.4 | 0 | 100 |
| 11 | 3 | 42.7 | 54.7 | ||
| 12 | 4 | 50.7 | 46.2 |
Embodiment five:
Use 0.1 gram silica alumina ratio (SiO
2/ Al
2O
3) be that 25 industrial Hydrogen β Si-Al molecular sieve replaces the 5%Ru/C catalyzer, the reaction times is 20 minutes, and temperature of reaction is 125 ℃, and other condition is all with embodiment one.Reaction result sees Table 5.
Table 5 has that β Si-Al molecular sieve catalysis CNNP decomposes contrast under anhydrous existence and the 125 ℃ of conditions
| Test number | First set reaction amount of water (Wt%) | The catalyst recirculation number of times | CNNP content (mmol/Kg) before the reaction | Reaction back CNNP content (mmol/Kg) | CNNP transformation efficiency (%) |
| 1 | 50 | 0 | 94.4 | 1.3 | 98.6 |
| 2 | 3 | 9.3 | 90.1 | ||
| 3 | 60 | 16.7 | 82.3 | ||
| 4 | 0 | 0 | 94.4 | 0 | 100 |
| 5 | 3 | 52.7 | 44.2 | ||
| 6 | 4 | 60.7 | 36.7 |
Embodiment six:
Use 0.5 gram silica alumina ratio (SiO
2/ Al
2O
3) be that 25 industrial Hydrogen β Si-Al molecular sieve replaces the 5%Ru/C catalyzer, other condition is all with embodiment one.Reaction result sees Table 6.
Table 6 has increases β Si-Al molecular sieve consumption catalysis CNNP decomposition contrast under the anhydrous existence condition
| Test number | First set reaction amount of water (Wt%) | The catalyst recirculation number of times | CNNP content (mmol/Kg) before the reaction | Reaction back CNNP content (mmol/Kg) | CNNP transformation efficiency (%) |
| 1 | 50 | 0 | 94.4 | 0.0 | 100 |
| 2 | 3 | 0.8 | 99.1 | ||
| 3 | 20 | 4.1 | 95.6 | ||
| 4 | 0 | 0 | 94.4 | 0 | 100 |
| 5 | 3 | 42.70 | 54.7 | ||
| 6 | 4 | 50.70 | 46.3 |
Claims (8)
1. the method for a catalytic decomposition of cyclohexane hydroperoxide in the presence of polar solvent, is carried out catalytic decomposition with solid catalyst, and key step is:
A) reaction substrate is the cyclohexane solution that contains cyclohexyl hydroperoxide, and catalyzer is loaded catalyst, acid molecular sieve catalyst or MCM-41 molecular sieve catalyst, and the add-on of catalyzer is counted 0.5-5% by the reactant solution gross weight; Add polar solvent water or organic alcohol, wherein the add-on of water is the 10-50% of reaction soln gross weight; The add-on of organic alcohol is the 0.1-5% of reaction soln gross weight;
B) reaction pressure is 0.1-0.6Mpa, and temperature of reaction 60-170 ℃, heated and stirred, stirring velocity are 50-1500 rev/min, and resultant of reaction is taken out in cooling after constant temperature 10-60 minute;
C) reclaiming catalyzer reuses.
2. the method for claim 1, the weight percent that it is characterized in that containing in the described reaction substrate cyclohexyl hydroperoxide is 0.5-50%.
3. the method for claim 1, it is characterized in that active constituent is cobalt, iron, ruthenium or gold in the described loaded catalyst, carrier is aluminum oxide, silicon oxide, zirconium white, gac or molecular sieve, and wherein active constituent content is counted 0.1-10% with total catalyst weight;
Described acid molecular sieve catalyst is the Hydrogen beta molecular sieve;
Contain Co, Cr active constituent in the skeleton of described MCM-41 molecular sieve, this active constituent content is counted 0.1-2% with total catalyst weight.
4. method as claimed in claim 3 is characterized in that the content of active constituent in the described loaded catalyst is counted 1-5% with total catalyst weight.
5. the method for claim 1 is characterized in that described organic alcohol is ethanol, methyl alcohol or Virahol.
6. the method for claim 1 is characterized in that described stirring velocity is 50-300 rev/min.
7. the method for claim 1 is characterized in that described temperature of reaction is 80-130 ℃.
8. the method for claim 1 is characterized in that, described being reflected under the nitrogen atmosphere carried out.
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| CN102641734B (en) * | 2011-02-18 | 2014-08-20 | 中国石油化工集团公司 | Catalyst for aryl hydrogen peroxide hydrogenation reduction and preparation and application thereof |
| CN102911026A (en) * | 2011-08-03 | 2013-02-06 | 中国科学院大连化学物理研究所 | Application of multi-phase catalyst in decomposition of cyclohexyl hydroperoxide |
| CN103372462B (en) * | 2012-04-26 | 2016-03-23 | 中国科学院大连化学物理研究所 | A kind of decomposing cycloalkyl hydrogen peroxide water-soluble catalytic agent system and application |
| CN106268847A (en) * | 2015-06-08 | 2017-01-04 | 中国石油化工股份有限公司 | The preparation of a kind of cyclohexane oxide solution decomposition catalyst and decomposition technique |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4491637A (en) * | 1982-06-11 | 1985-01-01 | Basf Aktiengesellschaft | Cobalt-containing supported catalysts and their preparation |
| CN1314885A (en) * | 1998-08-26 | 2001-09-26 | 纳幕尔杜邦公司 | Hydroperoxide decomposition process |
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| US4491637A (en) * | 1982-06-11 | 1985-01-01 | Basf Aktiengesellschaft | Cobalt-containing supported catalysts and their preparation |
| CN1314885A (en) * | 1998-08-26 | 2001-09-26 | 纳幕尔杜邦公司 | Hydroperoxide decomposition process |
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