CN1296333C - Process for catalytic decomposition of cyclohexane hydroperoxide - Google Patents
Process for catalytic decomposition of cyclohexane hydroperoxide Download PDFInfo
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- CN1296333C CN1296333C CNB2004100688732A CN200410068873A CN1296333C CN 1296333 C CN1296333 C CN 1296333C CN B2004100688732 A CNB2004100688732 A CN B2004100688732A CN 200410068873 A CN200410068873 A CN 200410068873A CN 1296333 C CN1296333 C CN 1296333C
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- molecular sieve
- reaction
- cyclohexane
- catalyst
- hydroperoxide
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Abstract
The present invention relates to a process for the catalytic decomposition of cyclohexane hydroperoxide. A beta type molecular sieve is used as a catalyst. Under a condition of a liquid phase, the cyclohexane hydroperoxide is converted into cyclohexanol and cyclohexanone. The catalyst and a cyclohexane solution of the cyclohexane hydroperoxide are stirred to the temperature rising to 50 to 150 DEG C at 50 to 1500 revolutions per minute at 0.1 to 1Mpa, and the use level of the catalyst is from 0.05 to 5% measured by the total weight of a reactant solution. Reaction products are taken out after the thermostatic reaction of 0.1 to 5 hours. Compared with the existing catalyst for the catalytic decomposition of the cyclohexane hydroperoxide, such as load type precious metal catalysts or transitional metal type catalysts, the catalyst used by the present invention has the characteristics of low price, easy acquirement, easy use, etc.
Description
Technical field
The present invention relates to a kind of cyclohexane solution that contains cyclohexyl hydroperoxide, under the beta molecular sieve katalysis, make wherein cyclohexyl hydroperoxide be converted into the method for hexalin and pimelinketone.
Technical background
The cyclohexyl hydroperoxide decomposition reaction is that cyclohexane oxidation prepares one of important step in hexalin and the pimelinketone process.
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.Shortcomings such as there is the cost height in this method, generates a large amount of alkaline waste waters and contaminate environment, and etching apparatus and yield are 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 brill, copper and iron), precious metal (as ruthenium) catalyst decomposes cyclohexyl hydroperoxide in patent WO 200024698.
Dupont (Du Pond) company has proposed to use the Au/Al that modifies through organosilicon in patent WO 200216296
2O
3Decompose cyclohexyl hydroperoxide.
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.
Do not see at present that use does not contain the pure molecular sieve decomposition cyclohexyl hydroperoxide report of transition metal or precious metal.Main purpose of the present invention is to use the beta molecular sieve solid catalyst to decompose cyclohexyl hydroperoxide, preparation hexalin and pimelinketone.
Summary of the invention
According to the present invention, reaction substrate is the cyclohexyl hydroperoxide cyclohexane solution.This solution is obtained by cyclohexane oxidation (or oxidation liquid is concentrated through distilling).In this solution contained cyclohexyl hydroperoxide amount by weight percentage, generally between 0.1%-10%.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 catalyzer is a beta molecular sieve.This beta molecular sieve mainly is meant Hydrogen acidic beta molecular sieve.The silica alumina ratio of this molecular sieve is pressed SiO
2/ Al
2O
3Meter is generally 10-100, is preferably 15-60; Na
2O content is counted 0.01-0.5% with total catalyst weight, is preferably 0.04-0.3%.
According to the present invention, employed beta-molecular sieve is meant the molecular sieve that the common synthesis method of being familiar with of being announced by the US3308069 of U.S. Mobile house journal the earliest of people obtains.The basic synthetic method of Hydrogen beta-molecular sieve is: being respectively silicon, aluminium source with silica gel, sodium aluminate etc., is template with the tetraethyl-oxyammonia, at first makes the former powder of sodium type beta-molecular sieve under certain hydrothermal condition.With the former powder of sodium type beta-molecular sieve 500 ℃ of-700 ℃ of following roastings, again through ammonium chloride exchange and once more step such as roasting make.At petroleum chemical industry, Hydrogen (or through add rare earth element, transition element is improved) beta-molecular sieve is often used as solid acid catalyst, is used for hydrocracking or alkylation reaction of arene.As be used for the Hydrogen beta-molecular sieve that catalysis benzene and ethylene reaction prepare ethylbenzene.
The above-mentioned main spectral line parameter of molecular sieve in x-ray diffraction spectra of the present invention is generally shown in the table 1.
The main spectral line parameter of the used beta molecular sieve X-ray of table 1 the present invention diffraction spectra
| Peak number | 2 θ values (°) | D value (A O) | I/I OValue |
| 1 | 7.65 | 11.62±0.23 | 52 |
| 2 | 11.70 | 7.55±0.13 | 5 |
| 3 | 20.81 | 4.11±0.10 | 15 |
| 4 | 22.46 | 3.90±0.13 | 100 |
| 5 | 26.85 | 3.32±0.05 | 15 |
| 6 | 29.51 | 3.00±0.06 | 14 |
| 7 | 42.45 | 2.05±0.07 | 8 |
Annotate: 2 θ values are diffraction angle, and the D value is a spacing, I/I
OValue is relative diffracted intensity
According to the present invention, the consumption of Hydrogen beta-molecular sieve, but is preferably between the 0.1-3% between 0.05-5% by the reaction substrate solution 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.Reaction pressure can be 0.1-10MPa according to temperature of reaction.
According to the present invention, cross decomposition reaction and can between 50-150 ℃, carry out.But be preferably between 80-130 ℃ isothermal reaction 0.1-5 hour.
Embodiment
Following example will specify specific implementation method of the present invention.
Embodiment one:
In 50 milliliters of stainless steel cauldrons that a charged magnetic stirs, add 0.1 gram silica alumina ratio and press SiO
2/ Al
2O
3Count 11.5, Na
2O content is 0.1%, industrial Hydrogen beta-molecular sieve.Add 10 again and restrain the cyclohexane solution that contains cyclohexyl hydroperoxide 2.1%.Reactor earlier with behind the nitrogen replacement, is fastened the air valve door again, and heat temperature raising to 85 ℃ continues isothermal reaction and lower the temperature after 20 minutes, the taking-up resultant of reaction while stirring.
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 weight percent concentration (Wt%) in the initial feed)-(CNNP weight percent concentration (Wt%) in the product)/(CNNP weight percent concentration (Wt%) in the initial feed)
Test-results sees Table 2.
Embodiment two:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 25, Na
2O content is 0.075% the industrial Hydrogen beta-molecular sieve of 0.1 gram, repeats embodiment one test, and its result one is listed in table 2.
Embodiment three:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 25, Na
2O content is 0.045% the industrial Hydrogen beta-molecular sieve of 0.1 gram, repeats embodiment one test, and its result one is listed in table 2.
Embodiment four:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 25, Na
2O content is 0.3% the industrial Hydrogen beta-molecular sieve of 0.1 gram, repeats embodiment one test, and its result one is listed in table 2.
Embodiment five:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 35, Na
2O content is 0.045% the industrial Hydrogen beta-molecular sieve of 0.1 gram, repeats embodiment one test, and its result one is listed in table 2.
Embodiment six:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 50, Na
2O content is 0.1% the industrial Hydrogen beta-molecular sieve of 0.1 gram, repeats embodiment one test, and its result one is listed in table 2.
Table 2 uses multiple model Hydrogen beta-molecular sieve catalysis cyclohexyl hydroperoxide (CNNP) decomposition reaction result
| The embodiment numbering | The Hydrogen beta-molecular sieve is formed | CNNP initial content (Wt%) | The final content of CNNP (Wt%) | CNNP rate of decomposition (%) | |
| SiO 2/Al 2O 3(mol/ mol) | Na 2O(Wt ％) | ||||
| 1 | 11.5 | 0.1 | 2.1 | 0.75 | 64.2 |
| 2 | 25 | 0.075 | 2.1 | 0.41 | 80.5 |
| 3 | 25 | 0.045 | 2.1 | 0.32 | 84.7 |
| 4 | 25 | 0.3 | 2.1 | 0.86 | 59.0 |
| 5 | 35 | 0.1 | 2.1 | 0.52 | 75.2 |
| 6 | 50 | 0.1 | 2.1 | 0.37 | 82.4 |
Embodiment seven:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 25, Na
2O content is 0.045% the industrial Hydrogen beta-molecular sieve of 0.05 gram, repeats embodiment one test, and it the results are shown in table 3.
Embodiment eight:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 25, Na
2O content is 0.045% the industrial Hydrogen beta-molecular sieve of 0.01 gram, repeats embodiment one test, and its result one is listed in table 3.
Embodiment nine:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 25, Na
2O content is 0.045% the industrial Hydrogen beta-molecular sieve of 0.1 gram, and temperature of reaction is 125 ℃, and other condition is with embodiment one test, and its result one is listed in table 3.
Embodiment ten:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 25, Na
2O content is 0.045% the industrial Hydrogen beta-molecular sieve of 0.1 gram, and reaction raw materials is the cyclohexane solution that 10 grams contain cyclohexyl hydroperoxide about 0.6%, and other condition is with embodiment one test, and its result one is listed in table 3.
Embodiment 11:
Use silica alumina ratio to press SiO
2/ Al
2O
3Count 25, Na
2O content is 0.045% the industrial Hydrogen beta-molecular sieve of 0.1 gram, and reaction raw materials is the cyclohexane solution that 10 grams contain cyclohexyl hydroperoxide about 3.8%, and other condition is with embodiment one test, and its result one is listed in table 3.
Catalysis CNNP decomposition reaction result under the different Hydrogen beta-molecular sieve of table 3 consumption, temperature of reaction and the mistake content
| The embodiment numbering | Beta-molecular sieve consumption (Wt%) | Temperature of reaction (℃) | CNNP initial content (Wt%) | The final content of CNNP (Wt%) | CNNP rate of decomposition (%) |
| 4 | 1 | 85 | 2.1 | 0.32 | 84.7 |
| 7 | 0.5 | 85 | 2.1 | 0.55 | 73.8 |
| 8 | 0.1 | 85 | 2.1 | 0.64 | 69.5 |
| 9 | 1 | 125 | 2.1 | 0.00 | 100 |
| 10 | 1 | 85 | 0.6 | 0.08 | 86.8 |
| 11 | 1 | 85 | 3.8 | 0.67 | 81.5 |
Claims (9)
1, a kind of process for catalytic decomposition of cyclohexane hydroperoxide is characterized in that, is catalyzer with the Hydrogen beta molecular sieve, under liquid-phase condition, cyclohexyl hydroperoxide is converted into hexalin and pimelinketone:
The cyclohexane solution of catalyzer and cyclohexyl hydroperoxide in 0.1-10Mpa, is warming up to 50-150 ℃ with 50-1500 rev/min of stirring, after isothermal reaction 0.1-5 hour, takes out resultant of reaction;
Described catalyst levels is counted 0.05-5% by the reactant solution gross weight.
2. according to the method for claim 1, it is characterized in that containing the cyclohexyl hydroperoxide weight percent in the cyclohexane solution of described cyclohexyl hydroperoxide is 0.1-10%.
3. according to the method for claim 1, it is characterized in that described catalyst levels is counted 0.1-3% by the reactant solution gross weight.
4. according to the method for claim 1, it is characterized in that, described beta molecular sieve, diffraction angle 2 θ in its x-ray diffraction spectra are: 7.65,11.70,20.81,22.46,26.85,29.51,42.45.
5. according to the method for claim 1 or 4, it is characterized in that described beta molecular sieve, SiO
2/ Al
2O
3Mol ratio is 10-100, Na
2O content is counted 0.01-0.5% with total catalyst weight.
6. according to the method for claim 5, it is characterized in that described beta molecular sieve, SiO
2/ Al
2O
3Mol ratio is 15-60, Na
2O content is counted 0.04-0.3% with total catalyst weight.
7. according to the method for claim 1, it is characterized in that described temperature of reaction is 80-130 ℃.
8. according to the method for claim 1, it is characterized in that described stirring velocity is 50-300 rev/min.
9. according to the method for claim 1, it is characterized in that described reaction is to carry out in nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100688732A CN1296333C (en) | 2004-07-13 | 2004-07-13 | Process for catalytic decomposition of cyclohexane hydroperoxide |
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|---|---|---|---|
| CNB2004100688732A CN1296333C (en) | 2004-07-13 | 2004-07-13 | Process for catalytic decomposition of cyclohexane hydroperoxide |
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| CN1296333C true CN1296333C (en) | 2007-01-24 |
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| CN107162014B (en) * | 2017-07-04 | 2020-06-26 | 江西师范大学 | Tin-silicon molecular sieve, preparation method thereof and method for catalytic oxidation of cyclohexane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4491637A (en) * | 1982-06-11 | 1985-01-01 | Basf Aktiengesellschaft | Cobalt-containing supported catalysts and their preparation |
| US4543427A (en) * | 1982-06-11 | 1985-09-24 | Basf Aktiengesellschaft | Preparation of cyclohexanol and cyclohexanone |
| CN1063419C (en) * | 1994-04-22 | 2001-03-21 | 肖藻生 | process for preparing cyclohexanol and cyclohexanone from cyclohexane |
| CN1443742A (en) * | 2003-03-21 | 2003-09-24 | 中国石化集团巴陵石油化工有限责任公司 | Decomposition method of cyclohexyl hydroperoxide |
| CN1454199A (en) * | 2000-08-18 | 2003-11-05 | 纳幕尔杜邦公司 | Improved hydroperoxide decomposition catalyst |
-
2004
- 2004-07-13 CN CNB2004100688732A patent/CN1296333C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4491637A (en) * | 1982-06-11 | 1985-01-01 | Basf Aktiengesellschaft | Cobalt-containing supported catalysts and their preparation |
| US4543427A (en) * | 1982-06-11 | 1985-09-24 | Basf Aktiengesellschaft | Preparation of cyclohexanol and cyclohexanone |
| CN1063419C (en) * | 1994-04-22 | 2001-03-21 | 肖藻生 | process for preparing cyclohexanol and cyclohexanone from cyclohexane |
| CN1454199A (en) * | 2000-08-18 | 2003-11-05 | 纳幕尔杜邦公司 | Improved hydroperoxide decomposition catalyst |
| CN1443742A (en) * | 2003-03-21 | 2003-09-24 | 中国石化集团巴陵石油化工有限责任公司 | Decomposition method of cyclohexyl hydroperoxide |
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