CN102179265A - Catalyst for use in preparation of cyclohexanol and cyclohexanone and method for preparing cyclohexanol and cyclohexanone - Google Patents
Catalyst for use in preparation of cyclohexanol and cyclohexanone and method for preparing cyclohexanol and cyclohexanone Download PDFInfo
- Publication number
- CN102179265A CN102179265A CN 201110063244 CN201110063244A CN102179265A CN 102179265 A CN102179265 A CN 102179265A CN 201110063244 CN201110063244 CN 201110063244 CN 201110063244 A CN201110063244 A CN 201110063244A CN 102179265 A CN102179265 A CN 102179265A
- Authority
- CN
- China
- Prior art keywords
- cyclohexanone
- cyclohexanol
- cyclohexane
- catalyst
- nano silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for use in the preparation of cyclohexanol and cyclohexanone, which comprises cobalt naphthenate and nano silicon dioxide, wherein the mass ratio of the cobalt to the nano silicon dioxide in the cobalt naphthenate is 1:(500 to 10,000). The invention also provides a method for preparing cyclohexanol and cyclohexanone, which comprises the following step: performing the oxidization reaction of cyclohexane and oxygen in the presence of the catalyst prepared according to the technical scheme; and obtaining cyclohexanol and cyclohexanone. Experiments show that when the catalyst provided by the invention is used for catalyzing the oxidization of cyclohexane for forming cyclohexanol and cyclohexanone, the cyclohexanol and cyclohexanone selectivity reaches 90.5 percent under the condition that the cyclohexane conversion rate is 4.2 percent, and the cyclohexane conversion rate reaches 8.5 percent when the cyclohexanol and cyclohexanone selectivity is 84.7 percent.
Description
Technical field
The invention belongs to the catalytic synthetic techniques field, relate in particular to a kind of preparation method who is used to prepare catalyst and a kind of cyclohexanol and the cyclohexanone of cyclohexanol and cyclohexanone.
Background technology
Cyclohexanol has another name called hexahydrophenol, and English name is cyclohexanol, and the CAS accession number is 108-93-0, and molecular formula is C
6H
12O; Cyclohexanone, English name are cyclohexanone, and the CAS accession number is 108-94-1, and molecular formula is C
6H
10O.Cyclohexanol and cyclohexanone all are important industrial chemicals, as, be the main intermediate of producing adipic acid and caprolactam, and adipic acid and caprolactam are the primary raw materials of producing nylon; Cyclohexanol and cyclohexanone also are the essential industry solvents, as are used for paint, coating etc.
The mixture of cyclohexanol and cyclohexanone is commonly called as KA oil, is generally prepared by cyclohexane oxidation.Cyclohexane oxidation prepares cyclohexanol and cyclohexanone generally comprises catalytic oxidation and non-catalyst oxidation method, catalytic oxidation is meant that cyclohexane oxidation under the effect of catalyst generates cyclohexanol and cyclohexanone, and oxidant commonly used comprises solubility cobalt salt, nano ferrite, supported the AIPO-5 molecular sieve of Ce, monokaryon bipyridyl copper complex etc.; The non-catalyst oxidation method is a kind of technology of Dutch Stamicarbon B.V. (DSM) exploitation, at first in the reactor of sodium pyrophosphate Passivation Treatment, cyclohexane is oxidized to cyclohexane peroxide (CHHP) under high temperature, condition of high voltage, then cyclohexane peroxide catalytic decomposition under alkali condition is generated cyclohexanol and cyclohexanone.
Prepare in the process of cyclohexanol and cyclohexanone at cyclohexane oxidation, cyclohexane is big by bond energy, the less C-C key of polarity is connected with c h bond and forms, and activation is difficulty comparatively, and reactivity is lower; On the other hand, because the activation of oxygen atom, oxidation product cyclohexanol and cyclohexanone have higher reactivity than cyclohexane, and over oxidation takes place easily, thereby reduce the selectivity of target product.Studies show that, under high-temperature and high-pressure conditions, 1 percentage point of the every raising of conversion of cyclohexane, the selectivity of cyclohexanol and cyclohexanone will descend 4 percentage points.Therefore, in order to guarantee the high selectivity of cyclohexanol and cyclohexane, conversion of cyclohexane need be controlled at reduced levels.As with the solubility cobalt salt, when generating cyclohexanol and cyclohexanone for the catalyst cyclohexane oxidation as cobalt naphthenate, cobalt octoate, cobaltous octadecanate and cobalt oleate etc., for the selectivity that guarantees cyclohexanol and cyclohexanone more than 80%, the conversion per pass of cyclohexane need be controlled in 4%.And be raw material with the cyclohexane, when adopting non-catalyst oxidation technology to prepare cyclohexanol and cyclohexanone, not only need the reaction condition of high temperature, high pressure, and the selectivity of cyclohexanol and cyclohexanone reaching at 80% o'clock, conversion of cyclohexane also only is 3.5%～4%.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method who is used to prepare catalyst and a kind of cyclohexanol and the cyclohexanone of cyclohexanol and cyclohexanone, when catalyst provided by the invention is used for catalysis cyclohexane oxidation generation cyclohexanol and cyclohexanone, have advantages of high catalytic activity and catalytic efficiency, cyclohexanol that obtains and cyclohexanone selectivity are higher, and conversion of cyclohexane is higher.
The invention provides a kind of catalyst that is used to prepare cyclohexanol and cyclohexanone, comprise cobalt naphthenate and nano silicon, the cobalt in the described cobalt naphthenate and the mass ratio of nano silicon are 1: 500～10000.
Preferably, described nano silicon is the nano silicon of modifying through organosilan.
Preferably, the mass ratio of cobalt in the described cobalt naphthenate and nano silicon is 1: 500～5000.
The present invention also provides the preparation method of a kind of cyclohexanol and cyclohexanone, may further comprise the steps:
Under the catalytic action of the described catalyst of technique scheme, cyclohexane and oxygen or air generation oxidation reaction obtain cyclohexanol and cyclohexanone.
Preferably, the mass ratio of described catalyst and described cyclohexane is 0.5～5: 100.
Preferably, the mass ratio of described catalyst and described cyclohexane is 1～4: 100.
Preferably, the temperature of described oxidation reaction is 120 ℃～160 ℃.
Preferably, the pressure of described oxidation reaction is 0.3MPa～5MPa.
Preferably, the time of described oxidation reaction is 0.5h～5h.
Preferably, described cyclohexane and oxygen or air carry out oxidation reaction under stirring condition.
Compared with prior art, the invention provides a kind of catalyst that is used to prepare cyclohexanol and cyclohexanone, comprise cobalt naphthenate and nano silicon, the cobalt in the described cobalt naphthenate and the mass ratio of nano silicon are 1: 500～10000.Catalyst provided by the invention has advantages of high catalytic activity and catalytic efficiency, be used for the process performance composite catalyzing effect that the catalysis cyclohexane oxidation generates cyclohexanol and cyclohexanone, under the higher prerequisite of retaining ring hexanol and cyclohexanone selectivity, improve conversion of cyclohexane, thereby improve the productive rate of cyclohexane and cyclohexanone.Experiment shows that when catalyst provided by the invention was used for catalysis cyclohexane oxidation generation cyclohexanol and cyclohexanone, when conversion of cyclohexane was 4.2%, the selectivity of cyclohexanol and cyclohexanone can reach 90.5%; When the selectivity of cyclohexanol and cyclohexanone was 84.7%, conversion of cyclohexane can reach 8.5%.
The specific embodiment
The invention provides a kind of catalyst that is used to prepare cyclohexanol and cyclohexanone, comprise cobalt naphthenate and nano silicon, the cobalt in the described cobalt naphthenate and the mass ratio of nano silicon are 1: 500～10000.
Cobalt naphthenate can be used for the catalysis cyclohexane oxidation and generate cyclohexanol and cyclohexanone, when still using cobalt naphthenate separately, can't reach all higher purpose of selectivity of conversion of cyclohexane and cyclohexanol and cyclohexanone.The present invention forms composite catalyst with nano silicon and cobalt naphthenate, the catalytic oxidation of common catalysis cyclohexane.
The present invention does not have particular restriction to described cobalt naphthenate, and the cobalt naphthenate of Gou Maiing gets final product from the market.
Described nano silicon is the former powder of nano silicon or through the nano silicon that organosilan is modified, and is preferably the nano silicon of modifying through organosilan, and described organosilan is preferably HMDS or dichlorodimethylsilane etc.The described nano silicon of modifying through organosilan is preparation in accordance with the following methods preferably:
Nano silicon is refluxed in organosilan solution, can obtain the nano silicon of modifying through organosilan.
In described catalyst, the cobalt in the described cobalt naphthenate and the mass ratio of described nano silicon are 1: 500～10000, more preferably 1: 500～5000, most preferably be 1: 1000～and 2000.
Nano silicon and cobalt naphthenate are mixed in organic solution, can obtain catalyst of the present invention after the drying.
Described catalyst has advantages of high catalytic activity and catalytic efficiency, can be used for the catalysis cyclohexane oxidation and prepare cyclohexanol and cyclohexanone, under the higher prerequisite of retaining ring hexanol and cyclohexanone selectivity, improve conversion of cyclohexane, thereby improve the productive rate of cyclohexane and cyclohexanone.
Catalyst of the present invention is used for the catalysis cyclohexane oxidation and prepares cyclohexanol and cyclohexanone, may further comprise the steps:
Under the catalytic action of the described catalyst of technique scheme, cyclohexane and oxygen or air generation oxidation reaction obtain cyclohexanol and cyclohexanone.
Add cyclohexane and the described catalyst of technique scheme in reactor after, aerating oxygen or air in reactor make cyclohexane under the effect of catalyst and oxygen oxidation take place, and generate cyclohexanol and cyclohexanone.
In the present invention, the mass ratio of described catalyst and described cyclohexane is preferably 0.5～5: 100, more preferably 1～4: 100, most preferably be 2～3: 100.
In the present invention, the temperature that described cyclohexane carries out oxidation reaction is preferably 120 ℃～160 ℃, more preferably 130 ℃～150 ℃, most preferably is 135 ℃～145 ℃.
In the present invention, the pressure that described cyclohexane carries out oxidation reaction is preferably 0.3MPa～5MPa, and more preferably 0.5MPa～4MPa most preferably is 1MPa～3MPa.
In the present invention, the time that described cyclohexane carries out oxidation reaction is preferably 0.5h～5h, and more preferably 1h～4h most preferably is 2h～3h.
In order to make catalyst bring into play better catalytic action, described cyclohexane preferably under stirring condition with oxygen generation oxidation reaction.
In cyclohexane oxidation process, cobalt naphthenate and the effect of nano silicon performance composite catalyzing are being kept under the higher prerequisite of cyclohexanol and cyclohexanone selectivity, improve conversion of cyclohexane, thereby improve the productive rate of cyclohexane and cyclohexanone.
After oxidation reaction finished, the present invention adopted following method that the reactant mixture that obtains is analyzed:
The reaction raw materials gross weight is designated as M0;
The reactant mixture that obtains after the reaction is weighed, be designated as M;
Take by weighing the reactant mixture of the first mass parts M1, with toluene is interior mark, adopt gas chromatography, analysis obtains the quality of cyclohexane, cyclohexanol, cyclohexanone and accessory substance, calculates the gross mass of cyclohexane, cyclohexanol, cyclohexanone and accessory substance among the reactant mixture M according to the proportionate relationship of M and M1;
Take by weighing the reactant mixture of the second mass parts M2, carry out titration with NaOH solution, the quality of the acids such as cyclohexylenedinitrilotetraacetic acid that determine to generate calculates the gross mass of acids such as cyclohexylenedinitrilotetraacetic acid among the reactant mixture M according to the proportionate relationship of M and M2;
The computational methods of conversion of cyclohexane are as follows:
(cyclohexane of cyclohexane raw material gross weight-volatilization-unreacted cyclohexane)/cyclohexane raw material gross weight * 100%;
Wherein, the cyclohexane quality of volatilization is M0-M.
The optionally computational methods of cyclohexanol and cyclohexanone are as follows:
The gross mass of cyclohexanol and cyclohexanone/(gross mass of the gross mass+cyclohexanol of accessory substance and the acids such as gross mass+cyclohexylenedinitrilotetraacetic acid of cyclohexanone) * 100%.
In the above-mentioned analytical method, owing to the cyclohexane of having considered to volatilize in the course of reaction and the acids such as cyclohexylenedinitrilotetraacetic acid of generation, therefore, the selectivity of conversion of cyclohexane that calculates and cyclohexanol and cyclohexanone and actual conversion and selectivity are comparatively approaching, and be more on the low side than conversion ratio and selectivity that existing method calculates.
Experiment shows that when catalyst provided by the invention was used for catalysis cyclohexane oxidation generation cyclohexanol and cyclohexanone, when conversion of cyclohexane was 4.2%, the selectivity of cyclohexanol and cyclohexanone can reach 90.5%; When the selectivity of cyclohexanol and cyclohexanone was 84.7%, conversion of cyclohexane can reach 8.5%.
In order to further specify the present invention, be used to prepare the catalyst of cyclohexanol and cyclohexanone and the preparation method of cyclohexanol and cyclohexanone is described in detail to provided by the invention below in conjunction with embodiment.
Below the raw materials used conventional chemical product of buying from the market that are among each embodiment, wherein, nano silicon is produced available from Zhejiang Hengdian Group, the trade mark is the nano silicon of JB258X type.
Embodiment 1
The 117mg cobalt naphthenate is mixed in ethanol with the 20g nano silicon, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 2000 a catalyst;
Described catalyst of 200mg and 15g cyclohexane are placed the 100mL reactor, with reactor fill oxygen to pressure be 1.0MPa, be warming up to 135 ℃, react 300min under the stirring condition, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows that conversion of cyclohexane is 4.2%, and the yield of cyclohexanol and cyclohexanone is 3.8%, and the selectivity of cyclohexanol and cyclohexanone is 90.5%.
Embodiment 2
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 20g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 2000 a catalyst;
Described catalyst of 200mg and 15g cyclohexane are placed the 100mL reactor, with reactor fill oxygen to pressure be 1.0MPa, be warming up to 135 ℃, react 120min under the stirring condition, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows that conversion of cyclohexane is 7.5%, and the yield of cyclohexanol and cyclohexanone is 6.4%, and the selectivity of cyclohexanol and cyclohexanone is 85.3%.
Embodiment 3
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 20g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 2000 a catalyst;
Described catalyst of 200mg and 15g cyclohexane are placed the 100mL reactor, with reactor fill oxygen to pressure be 0.6MPa, be warming up to 135 ℃, react 180min under the stirring condition, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows that conversion of cyclohexane is 7.0%, and the yield of cyclohexanol and cyclohexanone is 5.8%, and the selectivity of cyclohexanol and cyclohexanone is 82.8%.
Embodiment 4
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 20g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 2000 a catalyst;
Described catalyst of 200mg and 15g cyclohexane are placed the 100mL reactor, with reactor fill oxygen to pressure be 1.0MPa, be warming up to 145 ℃, react 90min under the stirring condition, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows that conversion of cyclohexane is 7.5%, and the yield of cyclohexanol and cyclohexanone is 6.2%, and the selectivity of cyclohexanol and cyclohexanone is 82.6%.
Embodiment 5
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 10g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 1000 a catalyst;
Described catalyst of 150mg and 15g cyclohexane are placed the 100mL reactor, with reactor fill oxygen to pressure be 1.0MPa, be warming up to 135 ℃, react 140min under the stirring condition, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows that conversion of cyclohexane is 8.5%, and the yield of cyclohexanol and cyclohexanone is 7.2%, and the selectivity of cyclohexanol and cyclohexanone is 84.7%.
Embodiment 6
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 5g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 500 a catalyst;
Described catalyst of 50mg and 15g cyclohexane are placed the 100mL reactor, with reactor fill oxygen to pressure be 1.0MPa, be warming up to 135 ℃, react 150min under the stirring condition, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows that conversion of cyclohexane is 7.8%, and the yield of cyclohexanol and cyclohexanone is 6.6%, and the selectivity of cyclohexanol and cyclohexanone is 84.6%.
Embodiment 7
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 5g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 500 a catalyst;
Described catalyst of 100mg and 15g cyclohexane are placed the 100mL reactor, with reactor fill oxygen to pressure be 1.0MPa, be warming up to 140 ℃, react 30min under the stirring condition, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows that conversion of cyclohexane is 6.9%, and the yield of cyclohexanol and cyclohexanone is 5.7%, and the selectivity of cyclohexanol and cyclohexanone is 82.6%.
Embodiment 8
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 5g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 500 a catalyst;
Described catalyst of 100mg and 15g cyclohexane are placed the 100mL reactor, and it is 1.5MPa that reactor is filled air to pressure, is warming up to 130 ℃, reacts 130min under the stirring condition, finishes reaction, obtains reaction product mixture.
Embodiment 9
The 117mg cobalt naphthenate is mixed in ethanol with the 100g nano silicon, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 10000 a catalyst.
Embodiment 10
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 100g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 10000 a catalyst.
Embodiment 11
The 117mg cobalt naphthenate is mixed in ethanol with the 5g nano silicon, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 500 a catalyst.
Embodiment 12
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 5g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 500 a catalyst.
Embodiment 13
The 117mg cobalt naphthenate is mixed in ethanol with the 50g nano silicon, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 5000 a catalyst.
Embodiment 14
With the nano silicon 2h that in mass concentration is the toluene solution of 0.5% HMDS, refluxes, obtain silanized silica;
The 117mg cobalt naphthenate is mixed in ethanol with the described silanized silica of 50g, and the mass ratio that stirs, obtains after the drying cobalt and nano silicon is 1: 5000 a catalyst.
Comparative example 1
200mg cobalt naphthenate and 15g cyclohexane are placed the 100mL reactor, with reactor fill oxygen to pressure be 1.0MPa, be warming up to 135 ℃, react 300min under the stirring condition, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows that conversion of cyclohexane is 3.8%, and the yield of cyclohexanol and cyclohexanone is 3.8%, and the selectivity of cyclohexanol and cyclohexanone is 80.2%.
By the foregoing description and comparative example 1 as can be known, when adopting catalyst cyclohexane oxidation provided by the invention to generate cyclohexanol and cyclohexanone, the selectivity of conversion of cyclohexane, cyclohexanol and cyclohexanone all increases.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a catalyst that is used to prepare cyclohexanol and cyclohexanone comprises cobalt naphthenate and nano silicon, and the cobalt in the described cobalt naphthenate and the mass ratio of nano silicon are 1: 500～10000.
2. catalyst according to claim 1 is characterized in that, described nano silicon is the nano silicon of modifying through organosilan.
3. catalyst according to claim 1 is characterized in that, the cobalt in the described cobalt naphthenate and the mass ratio of nano silicon are 1: 500～10000.
4. the preparation method of cyclohexanol and cyclohexanone may further comprise the steps:
Under the effect of any described catalyst of claim 1～3, cyclohexane and oxygen or air generation oxidation reaction obtain cyclohexanol and cyclohexanone.
5. preparation method according to claim 4 is characterized in that, the mass ratio of described catalyst and described cyclohexane is 0.5～5: 100.
6. preparation method according to claim 5 is characterized in that, the mass ratio of described catalyst and described cyclohexane is 1～4: 100.
7. preparation method according to claim 4 is characterized in that, the temperature of described oxidation reaction is 120 ℃～160 ℃.
8. preparation method according to claim 4 is characterized in that, the pressure of described oxidation reaction is 0.3MPa～5MPa.
9. preparation method according to claim 4 is characterized in that, the time of described oxidation reaction is 0.5h～5h.
10. preparation method according to claim 4 is characterized in that, described cyclohexane and oxygen or air carry out oxidation reaction under stirring condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110063244 CN102179265B (en) | 2011-03-16 | 2011-03-16 | Catalyst for use in preparation of cyclohexanol and cyclohexanone and method for preparing cyclohexanol and cyclohexanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110063244 CN102179265B (en) | 2011-03-16 | 2011-03-16 | Catalyst for use in preparation of cyclohexanol and cyclohexanone and method for preparing cyclohexanol and cyclohexanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102179265A true CN102179265A (en) | 2011-09-14 |
| CN102179265B CN102179265B (en) | 2013-04-10 |
Family
ID=44565665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110063244 Active CN102179265B (en) | 2011-03-16 | 2011-03-16 | Catalyst for use in preparation of cyclohexanol and cyclohexanone and method for preparing cyclohexanol and cyclohexanone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102179265B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563550A (en) * | 2019-08-30 | 2019-12-13 | 浙江工业大学 | Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/zinc (II) salt |
| CN110935450A (en) * | 2019-11-14 | 2020-03-31 | 广东工业大学 | Cobalt silicon oxide material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621398A (en) * | 2003-11-25 | 2005-06-01 | 肖藻生 | Method for preparing cyclohexanone and cyclohexanol by cyclohexane oxidation |
| CN1775717A (en) * | 2004-11-15 | 2006-05-24 | 中国科学院大连化学物理研究所 | Accelerating agent for cyclohexane liquid-phase air oxidation reaction and its use |
| CN101733164A (en) * | 2009-12-21 | 2010-06-16 | 中国科学院长春应用化学研究所 | Catalyst system for liquid-phase catalytic oxidization of cyclohexane for preparing cyclohexanol and cyclohexanone and using method thereof |
-
2011
- 2011-03-16 CN CN 201110063244 patent/CN102179265B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621398A (en) * | 2003-11-25 | 2005-06-01 | 肖藻生 | Method for preparing cyclohexanone and cyclohexanol by cyclohexane oxidation |
| CN1775717A (en) * | 2004-11-15 | 2006-05-24 | 中国科学院大连化学物理研究所 | Accelerating agent for cyclohexane liquid-phase air oxidation reaction and its use |
| CN101733164A (en) * | 2009-12-21 | 2010-06-16 | 中国科学院长春应用化学研究所 | Catalyst system for liquid-phase catalytic oxidization of cyclohexane for preparing cyclohexanol and cyclohexanone and using method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563550A (en) * | 2019-08-30 | 2019-12-13 | 浙江工业大学 | Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/zinc (II) salt |
| CN110935450A (en) * | 2019-11-14 | 2020-03-31 | 广东工业大学 | Cobalt silicon oxide material and preparation method and application thereof |
| CN110935450B (en) * | 2019-11-14 | 2022-10-21 | 广东工业大学 | Cobalt silicon oxide material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102179265B (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sloboda‐Rozner et al. | Aqueous Biphasic Oxidation: A Water‐Soluble Polyoxometalate Catalyst for Selective Oxidation of Various Functional Groups with Hydrogen Peroxide | |
| CN104607235B (en) | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation | |
| CN103254060B (en) | Method for preparing adipic acid through co-catalytic oxidation of six-carbon oxygenated compound and cyclohexane | |
| Piccinini et al. | Effect of the reaction conditions on the performance of Au–Pd/TiO 2 catalyst for the direct synthesis of hydrogen peroxide | |
| CN103586067B (en) | Method for synthesizing acrylic acid by aqueous formaldehyde solution and acetic acid | |
| JP7231740B2 (en) | Novel laurolactam production method and synthesis apparatus | |
| CN104817428A (en) | Method for production of cyclohexanol and cyclohexanone through selective oxidation of cyclohexane | |
| CN104974016B (en) | The method that hydrogenation on cinnamic aldehyde prepares cinnamyl alcohol | |
| CN109456176A (en) | Novel catalytic oxidation method of cycloparaffin promoted by copper porphyrin | |
| CN109456175A (en) | New zinc porphyrin promoted cycloparaffin catalytic oxidation method | |
| CN107879912A (en) | A kind of continuous production technology of the pentanone of 2 methyl of perfluor 3 | |
| CN104974047A (en) | Method for preparing aminostyrene through catalytic hydrogenation of nitrostyrene | |
| CN102179265B (en) | Catalyst for use in preparation of cyclohexanol and cyclohexanone and method for preparing cyclohexanol and cyclohexanone | |
| CN101733164A (en) | Catalyst system for liquid-phase catalytic oxidization of cyclohexane for preparing cyclohexanol and cyclohexanone and using method thereof | |
| CN104478677B (en) | A kind of method that bionic catalysis diphenyl-methane dioxygen oxidation prepares benzophenone | |
| Ni et al. | Binary catalytic systems constructed by porphyrin cobalts (II) with confining nano-region and Zn (OAc) 2 for oxygenation of cycloalkanes with O2 in relay mode | |
| TW201136907A (en) | Epoxidation of an olefin | |
| CN109369327A (en) | Novel nickel porphyrin-promoted cycloparaffin catalytic oxidation method | |
| Cancino et al. | Heterometallic Cu II/Ln III polymers active in the catalytic aerobic oxidation of cycloalkenes under solvent-free conditions | |
| CN106946668A (en) | A kind of method that phenol hydrogenation prepares cyclohexanone | |
| CN109678754B (en) | Preparation method of 11-cyanoundecanoic acid | |
| CN102725267B (en) | Method for producing alkyl hydroperoxide | |
| CN102617453A (en) | Method for preparing pyridine-4-formaldehyde | |
| CN107335448B (en) | A kind of AgCo nanocrystal and its catalyst, preparation method and application | |
| CN112321530A (en) | Preparation method of continuous synthetic rubber vulcanization accelerator CBS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |