CN102179265B - 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
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- CN102179265B CN102179265B CN 201110063244 CN201110063244A CN102179265B CN 102179265 B CN102179265 B CN 102179265B CN 201110063244 CN201110063244 CN 201110063244 CN 201110063244 A CN201110063244 A CN 201110063244A CN 102179265 B CN102179265 B CN 102179265B
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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 the preparation method of a kind of catalyst for the preparation of cyclohexanol and cyclohexanone and a kind 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 obtaining 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 being 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 refers to 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 Bipyridine-copper Complex etc.; The non-catalyst oxidation method is a kind of technique 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 connected with c h bond by bond energy C-C key large, that polarity is less 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 easily occurs, thereby reduce the selective of target product.Studies show that, under high-temperature and high-pressure conditions, 1 percentage point of the every raising of the conversion ratio of cyclohexane, cyclohexanol and cyclohexanone selectively will descend 4 percentage points.Therefore, in order to guarantee the high selectivity of cyclohexanol and cyclohexane, need to be with the conversion rate control of cyclohexane at reduced levels.As with the solubility cobalt salt, when generating cyclohexanol and cyclohexanone such as cobalt naphthenate, cobalt octoate, cobaltous octadecanate and cobalt oleate etc. for the catalyst cyclohexane oxidation, for guarantee cyclohexanol and cyclohexanone selectively more than 80%, the conversion per pass of cyclohexane need to be controlled in 4%.And take cyclohexane as raw material, when adopting non-catalyst oxidation technique to prepare cyclohexanol and cyclohexanone, not only need the reaction condition of high temperature, high pressure, and cyclohexanol and cyclohexanone selectively reach 80% the time, the conversion ratio 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 the preparation method of a kind of catalyst for the preparation of cyclohexanol and cyclohexanone and a kind of cyclohexanol and cyclohexanone, when catalyst provided by the invention is used for catalysis cyclohexane oxidation generation cyclohexanol and cyclohexanone, have higher catalytic activity and catalytic efficiency, the cyclohexanol that obtains and cyclohexanone are selectively higher, and the conversion ratio of cyclohexane is higher.
The invention provides a kind of catalyst for the preparation of 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 the 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 for the preparation of 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 higher catalytic activity and catalytic efficiency, be used for the process performance composite catalyzing effect of catalysis cyclohexane oxidation generation cyclohexanol and cyclohexanone, under retaining ring hexanol and the selective higher prerequisite of cyclohexanone, improve the conversion ratio of cyclohexane, thereby improve the productive rate of cyclohexane and cyclohexanone.Experiment shows, when catalyst provided by the invention is used for the catalysis cyclohexane oxidation and generates cyclohexanol and cyclohexanone, when the conversion ratio of cyclohexane is 4.2%, cyclohexanol and cyclohexanone selectively can reach 90.5%; When cyclohexanol and cyclohexanone selectively be 84.7% the time, the conversion ratio of cyclohexane can reach 8.5%.
The specific embodiment
The invention provides a kind of catalyst for the preparation of 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, but when using cobalt naphthenate separately, selective all higher purposes that can't reach the conversion ratio of cyclohexane and cyclohexanol and cyclohexanone.The present invention forms composite catalyst, the catalytic oxidation of co-catalysis cyclohexane with nano silicon and cobalt naphthenate.
The present invention does not have particular restriction to described cobalt naphthenate, and the cobalt naphthenate of buying from the market gets final product.
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 in accordance with the following methods preparation 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 higher catalytic activity and catalytic efficiency, can be used for the catalysis cyclohexane oxidation and prepare cyclohexanol and cyclohexanone, under retaining ring hexanol and the selective higher prerequisite of cyclohexanone, improve the conversion ratio 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.
After adding cyclohexane and the described catalyst of technique scheme in the reactor, in reactor, pass into oxygen or air, make cyclohexane under the effect of catalyst and oxygen, oxidation occur, 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 the condition that stirs with oxygen generation oxidation reaction.
In cyclohexane oxidation process, cobalt naphthenate and the effect of nano silicon performance composite catalyzing keeping under the selective higher prerequisite of cyclohexanol and cyclohexanone, improve the conversion ratio of cyclohexane, thereby improve the productive rate of cyclohexane and cyclohexanone.
After oxidation reaction was complete, the present invention adopted following methods 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, take toluene as 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 the acids such as cyclohexylenedinitrilotetraacetic acid among the reactant mixture M according to the proportionate relationship of M and M2;
The computational methods of the conversion ratio 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, selective and the actual conversion and selectively comparatively approaching of the conversion ratio of the cyclohexane that calculates and cyclohexanol and cyclohexanone, the conversion ratio that calculates than existing method and selectively on the low side.
Experiment shows, when catalyst provided by the invention is used for the catalysis cyclohexane oxidation and generates cyclohexanol and cyclohexanone, when the conversion ratio of cyclohexane is 4.2%, cyclohexanol and cyclohexanone selectively can reach 90.5%; When cyclohexanol and cyclohexanone selectively be 84.7% the time, the conversion ratio of cyclohexane can reach 8.5%.
In order to further specify the present invention, below in conjunction with embodiment the preparation method of the catalyst for the preparation of cyclohexanol and cyclohexanone provided by the invention and cyclohexanol and cyclohexanone is described in detail.
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 catalyst;
The 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 condition of stirring, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows, the conversion ratio of cyclohexane is 4.2%, and the yield of cyclohexanol and cyclohexanone is 3.8%, cyclohexanol and cyclohexanone selectively be 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 catalyst;
The 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 condition of stirring, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows, the conversion ratio of cyclohexane is 7.5%, and the yield of cyclohexanol and cyclohexanone is 6.4%, cyclohexanol and cyclohexanone selectively be 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 catalyst;
The 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 condition of stirring, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows, the conversion ratio of cyclohexane is 7.0%, and the yield of cyclohexanol and cyclohexanone is 5.8%, cyclohexanol and cyclohexanone selectively be 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 catalyst;
The 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 condition of stirring, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows, the conversion ratio of cyclohexane is 7.5%, and the yield of cyclohexanol and cyclohexanone is 6.2%, cyclohexanol and cyclohexanone selectively be 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 catalyst;
The 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 condition of stirring, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows, the conversion ratio of cyclohexane is 8.5%, and the yield of cyclohexanol and cyclohexanone is 7.2%, cyclohexanol and cyclohexanone selectively be 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 catalyst;
The 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 condition of stirring, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows, the conversion ratio of cyclohexane is 7.8%, and the yield of cyclohexanol and cyclohexanone is 6.6%, cyclohexanol and cyclohexanone selectively be 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 catalyst;
The 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 condition of stirring, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows, the conversion ratio of cyclohexane is 6.9%, and the yield of cyclohexanol and cyclohexanone is 5.7%, cyclohexanol and cyclohexanone selectively be 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 catalyst;
The 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 condition of stirring, 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 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 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 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 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 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 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 condition of stirring, finish reaction, obtain reaction product mixture.
According to analytical method mentioned above described reaction product mixture is analyzed, the result shows, the conversion ratio of cyclohexane is 3.8%, and the yield of cyclohexanol and cyclohexanone is 3.8%, cyclohexanol and cyclohexanone selectively be 80.2%.
By above-described embodiment and comparative example 1 as can be known, when adopting catalyst cyclohexane oxidation provided by the invention to generate cyclohexanol and cyclohexanone, selectively all the increasing of the conversion ratio of cyclohexane, cyclohexanol and cyclohexanone.
The above only is preferred embodiment 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. the catalyst for the preparation of 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 ~ 5000.
4. the preparation method of a cyclohexanol and cyclohexanone may further comprise the steps:
Under the effect of the described catalyst of claim 1 ~ 3 any one, 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.
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| 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 |
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| 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 |
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