CN101337878A - Method for directly producing adipic acid by cyclohexane catalytic oxidation - Google Patents
Method for directly producing adipic acid by cyclohexane catalytic oxidation Download PDFInfo
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Abstract
The invention discloses a method for directly producing adipic acid by catalytically oxidizing cyclohexane, which comprises the following steps: mixing cyclohexane, a solvent, an initiator and a carbon catalyst to form a mixed suspension, wherein the weight ratio of the solvent, the carbon catalyst, the initiator and cyclohexane is (0 to 99):(0.1 to 0.000125):(1 to 0.0005):1, and the carbon catalyst is carbon nanotube, graphite or active carbon; heating the mixed suspension to 50 to 250 DEG C; introducing oxygen or air as an oxidant; keeping the pressure in a reaction kettle at 0.1 to 5 MPa, and reacting for 0.1 to 20 h; and separating the reaction mixture to obtain the adipic acid product. The method can prevent environment pollution and corrosion of equipment due to the use of nitric acid, and can solve the problems such as the difficulties in recovering the homogeneous catalyst and deactivation of the homogeneous catalyst in the oxidization process of cyclohexane. No noble metal catalyst is used to reduce the catalyst cost, and the used catalyst can be recovered and used repeatedly.
Description
Technical field
The present invention relates to the production method of hexanodioic acid, particularly relate to a kind of method by directly producing adipic acid by cyclohexane catalytic oxidation.
Background technology
Hexanodioic acid is a kind of important chemical intermediate, is the important source material of preparation urethane and nylon 66.In traditional Production Processes of Adipic Acid, the first step oxidizing ethyle alkyl generates hexalin and pimelinketone (KA oil), and transformation efficiency is general＜and 10%, selectivity 70-90%, the product separating energy consumption is big, produces a large amount of waste lyes; Second step was oxidized to hexanodioic acid with nitric acid with KA oil, produced the oxynitrides that environment is had severe contamination in the production process, and is serious to equipment corrosion, the operational condition harshness.Therefore, the new process for producing of exploitation hexanodioic acid is the difficult point and the focus on scientific and technical boundary always.
In Chinese invention patent ZL 94110939.9, CN 1714069A and 95195040.1, all use the catalyst based catalyzed oxidation hexanaphthene of homogeneous cobalt, but such technology there are intermediate product cyclohexyl hydroperoxide and product ester to generate.
Chinese invention patent ZL200310110458.4, ZL03118249.6 and ZL200310110349.2 disclose the use metalloporphyrin and have made catalyzer, and air oxidation of cyclohexane prepares the method for hexanodioic acid.These class methods are the homogeneous catalysis process, the catalytic efficiency height, but metalloporphyrin type homogeneous catalyst is expensive, and can't reclaim and reuse.
The nanometer titanium dioxide ruthenium catalyzed oxidation hexanaphthene one that 200810026686.6 Chinese invention patent applications of applicant's application disclose load on the carbon nanotube goes on foot the method for preparing hexanodioic acid, this method joins hexanaphthene, solvent, initiator in the reactor with the solid catalyzer mixes, and forms mixed suspension; Be warming up to 50-250 ℃, the oxygen of feeding sufficient quantity or air are as oxygenant, and the reaction times is 0.1-20h; Reaction mixture is separated, obtain solid catalyst and the liquid mixture that contains reaction product, unreacted reactant and solvent; To isolate hexanodioic acid in the isolated liquid phase mixture.Catalyzer is the ru oxide of solid carrier load, and solid carrier is aluminum oxide, molecular sieve, carbon nanotube, silicon-dioxide, activated carbon, zeolite, sepiolite, porous ceramics or polyvinyl chloride; This catalyst efficient height, good stability, but use nanometer titanium dioxide ruthenium noble metal catalyst, cost is higher relatively.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of flow process simply, not use the method for the directly producing adipic acid by cyclohexane catalytic oxidation of noble metal catalyst, environmental protection.
The object of the present invention is achieved like this:
A kind of method of directly producing adipic acid by cyclohexane catalytic oxidation comprises the steps:
(1), forms mixed suspension with hexanaphthene, solvent, initiator and carbon material catalyst mix; The weight ratio of described solvent, carbon material catalyzer, initiator and hexanaphthene is 0-99: 0.000125-0.1: 0.0005-1: 1; The organic solvent of described solvent for mixing with hexanaphthene; Described carbon material catalyzer is carbon nanotube, graphite or gac; Described initiator is selected from one or more in tertbutyl peroxide, butanone, hexalin, the pimelinketone;
(2) step (1) gained mixing suspension is warming up to 50-250 ℃, aerating oxygen or air are as oxygenant, and keep-uping pressure is 0.1-5MPa, reaction 0.1-20h;
(3) step (2) reaction mixture is separated, obtain hexanodioic acid.
For further realizing the object of the invention, described carbon nanotube is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
The weight ratio of described carbon material catalyzer and hexanaphthene is preferably 0.00167-0.005: 1.
The temperature of reaction of described step (2) is preferably 100-200 ℃.
Describedly can be preferably acetone, methyl alcohol, acetonitrile or acetate with the organic solvent that hexanaphthene mixes.
Technology of the present invention can adopt operate continuously, also can adopt the batch-type periodical operation.
The present invention is a catalyzer with the carbon material, utilizes the air or oxygen directly producing adipic acid by cyclohexane catalytic oxidation.Compared with prior art, have the following advantages: (1) is used and is made catalyzer with carbon material, and raw material is easy to get, do not use noble metal catalyst, low price, catalytic activity height, catalyst stability is good, reacts to be heterogeneous catalysis process, catalyzer separate easily and recycling.(2) reaction conditions is gentle relatively, and oxygenant is an air or oxygen, environmental pollution and the equipment corrosion of having avoided the use of nitric acid to cause.(3) producing hexanodioic acid by hexanaphthene is direct catalytic oxidation of a step, and route is short, and technical process is simple.
Embodiment
The present invention is described further below in conjunction with embodiment, but the scope that protection scope of the present invention is not limited to represent among the embodiment.
Embodiment 1
The 237g hexanaphthene joined in the closed reaction kettle with multi-walled carbon nano-tubes with acetone, tertbutyl peroxide mix, form mixed suspension.Wherein, the weight ratio of acetone and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and multi-walled carbon nano-tubes is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 34: 1.This suspension under agitation is heated to 125 ℃, aerating oxygen is to 1.5MPa, because reaction process constantly consumes oxygen with stoichiometric ratio, so carry out in the process by the stable-pressure device and the continuous supplemental oxygen of under meter that link to each other with source of oxygen and keep-up pressure constant at 1.5MPa in reaction.React after 8 hours,, it is filtered, obtain solid catalyst and liquid phase mixture, this liquid phase mixture is analyzed to determine the transformation efficiency and the selectivity of reaction from Polycondensation Reactor and Esterification Reactor relief liquor solid-phase mixture.Analytical procedure is carried out according to patent CN1936586A disclosed method, wherein the analysis of hexanaphthene, pimelinketone, hexalin is carried out on Agilent 6820 gas-chromatographies that capillary column is housed, and the analysis of hexanodioic acid, Succinic Acid, pentanedioic acid is carried out on the Agilent1100 liquid chromatography.The separation of this liquid phase mixture and the purification of hexanodioic acid can be according to general known physics and chemical processes, adopt conventional decompress filter and recrystallization method in the present embodiment, can obtain purity and be 98.1% hexanodioic acid.
After reaction 8 hours, conversion of cyclohexane is up to 40%, and wherein the hexanodioic acid selectivity is greater than 60%, obviously is better than the effect of all kinds of solid catalysts reported in the document.Present embodiment utilizes multi-walled carbon nano-tubes to be catalyzer, is oxygenant with oxygen, under comparatively gentle condition the hexanaphthene oxidation step is become hexanodioic acid, the reactive activity height, and selectivity is good.Under up to 40% transformation efficiency, the product of degree of not meeting oxidation generates.Solid catalyst can separate easily to reuse.More favourable thing, present method have been avoided the use of nitric acid, thereby cause pollution and equipment corrosion to environment.
Embodiment 2～4
237g hexanaphthene and acetone, pimelinketone and multi-walled carbon nano-tubes joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetone and hexanaphthene is 1: 1.5, and hexanaphthene and multi-walled carbon nano-tubes weight ratio are 474: 1, and the weight ratio of hexanaphthene and pimelinketone is 40: 1.Should under agitation be heated to the temperature shown in the table 1 respectively by mixed suspension, aerating oxygen is to 1.5MPa, carries out in the process constantly supplemental oxygen and keep-ups pressure constant in 1.5Mpa in reaction.React after 8 hours,, it is filtered, obtain solid catalyst and liquid phase mixture, this liquid phase mixture is analyzed to determine the transformation efficiency and the selectivity of reaction from Polycondensation Reactor and Esterification Reactor relief liquor solid-phase mixture.The separation of product and analytical procedure be with embodiment 1, can obtain purity and be respectively 99.1%, 99.6%, 99.0% hexanodioic acid, reaction conversion ratio and selectivity such as following table 1.
Embodiment 2～4 shows, according to method of the present invention, can realize the catalyzed oxidation of hexanaphthene under lower temperature, and the selectivity of hexanodioic acid is more excellent in the resulting product.When temperature of reaction was 125 ℃ and 250 ℃, reaction conversion ratio was higher.Wherein can obtain more excellent hexanodioic acid selectivity in the time of 125 ℃, adipic acid yield surpasses 30% under this temperature.Proved that method of the present invention is applicable to preparing adipic acid by using cyclohexane catalytic oxidation one-step under the gentle condition.
Table 1 temperature of reaction is to the influence of cyclohexane oxidation
| Embodiment | 2 | 3 | 4 |
| Temperature of reaction (℃) | 50 | 125 | 250 |
| Cyclohexane conversion | 4％ | 53％ | 61％ |
| The hexanodioic acid selectivity | 24％ | 65％ | 34％ |
Embodiment 5
The acetone of 237g hexanaphthene and respective amount, pimelinketone and multi-walled carbon nano-tubes joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of solvent and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and multi-walled carbon nano-tubes is 474: 1, and the weight ratio of hexanaphthene and pimelinketone is 40: 1.Should under agitation be heated to 125 ℃ by mixed suspension, aerating oxygen reacted 8 hours to 1MPa, and the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 21%, and the hexanodioic acid selectivity is 28%.
Embodiment 6
The methyl alcohol of 237g hexanaphthene and respective amount, tertbutyl peroxide and multi-walled carbon nano-tubes joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of solvent and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and multi-walled carbon nano-tubes is 474: 1, and the weight ratio of hexanaphthene and pimelinketone is 40: 1.Should under agitation be heated to 125 ℃ by mixed suspension, aerating oxygen reacted 8 hours to 5MPa, and the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 56%, and the hexanodioic acid selectivity is 71%.
Embodiment 7
The acetone of 237g hexanaphthene and respective amount, pimelinketone and Single Walled Carbon Nanotube joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of ethanol and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and Single Walled Carbon Nanotube is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 40: 1.Should under agitation heat 125 ℃ by mixed suspension, aerating oxygen reacted 8 hours to certain pressure, and the separation of product and analytical procedure be with embodiment 1, reaction conversion ratio and selectivity such as following table 2.The raising reaction pressure helps the conversion of hexanaphthene, and transformation efficiency was higher when reaction pressure was 1.5MPa and 5MPa, and the selectivity of hexanodioic acid is best at 1.5MPa.
Table 2 reaction pressure is to the influence of cyclohexane oxidation
| Reaction pressure (MPa) | 1.0 | 1.5 | 5.0 |
| Cyclohexane conversion | 13％ | 57％ | 66％ |
| The hexanodioic acid selectivity | 17％ | 48％ | 58％ |
Embodiment 8
The methyl alcohol of 237g hexanaphthene and respective amount, tertbutyl peroxide and multi-walled carbon nano-tubes joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of methyl alcohol and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and multi-walled carbon nano-tubes is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 40: 1.This suspension under agitation is heated to 50 ℃, and aerating oxygen reacted 8 hours to 1.5MPa, and the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 1%, and the hexanodioic acid selectivity is 11%.
Embodiment 9
The methyl alcohol of 237g hexanaphthene and respective amount, tertbutyl peroxide and double-walled carbon nano-tube joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of methyl alcohol and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and double-walled carbon nano-tube is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 40: 1.This suspension under agitation is heated to 250 ℃, and aerating oxygen reacted 8 hours to 1.5MPa, and the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 43%, and the hexanodioic acid selectivity is 31%.
Embodiment 10
The acetonitrile of 5g hexanaphthene and respective amount, hexalin and multi-walled carbon nano-tubes joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetonitrile and hexanaphthene is 99: 1, and hexanaphthene and multi-walled carbon nano-tubes weight ratio are 10: 1, and the weight ratio of hexanaphthene and hexalin is 1: 1.This suspension under agitation is heated to 50 ℃, and aerating oxygen is to 5MPa, and behind the reaction certain hour, the separation of product and analytical procedure be with embodiment 1, reaction conversion ratio and selectivity such as following table 3.The transformation efficiency of reaction and selectivity all increase with the reaction times, and it is favourable therefore selecting the suitably long reaction times.
Table 3 reaction times is to the influence of cyclohexane oxidation
| Reaction times (hour) | 0.1 | 8 | 20 |
| Cyclohexane conversion | 0.3％ | 32％ | 41％ |
| The hexanodioic acid selectivity | 4％ | 21％ | 36％ |
Embodiment 11
The acetonitrile of 395g hexanaphthene and respective amount, hexalin and graphite joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetonitrile and hexanaphthene is 0: 1, and the weight ratio of hexanaphthene and graphite is 8000: 1, and the weight ratio of hexanaphthene and hexalin is 2000: 1.Should under agitation be heated to 125 ℃ by mixed suspension, aerating oxygen reacts after 8 hours to 1.5MPa, and the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 2%, and the hexanodioic acid selectivity is 14%.
Embodiment 12
The acetate of 350g hexanaphthene and respective amount, butanone and gac joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetate and hexanaphthene is 1: 9, and the weight ratio of hexanaphthene and gac is 50: 1, and the weight ratio of hexanaphthene and butanone is 99: 1.Should under agitation be heated to 250 ℃ by mixed suspension, aerating oxygen reacts after 8 hours to 5MPa, and the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 3%, and the hexanodioic acid selectivity is 13%.
Embodiment 13
The acetate of 350g hexanaphthene and respective amount, butanone and graphite catalyst joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetate and hexanaphthene is 1: 9, and the weight ratio of hexanaphthene and graphite is 50: 1, and the weight ratio of hexanaphthene and butanone is 99: 1.Should under agitation be heated to 50 ℃ by mixed suspension, bubbling air reacts after 8 hours to 0.1MPa, and the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 5%, and the hexanodioic acid selectivity is 17%.
Catalyst stability embodiment 1
(1) acetone of 237g hexanaphthene and respective amount, pimelinketone and multi-walled carbon nano-tubes catalyzer are joined in the airtight batch reactor and mix, form mixed suspension.Wherein, the weight ratio of acetone and hexanaphthene is 1: 1.5, the weight ratio of hexanaphthene and catalyzer is 474: 1, the weight ratio of hexanaphthene and pimelinketone is 40: 1, and this suspension under agitation is heated to 125 ℃, and aerating oxygen is to 1.5MPa, reacted 8 hours, the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 53%, and the hexanodioic acid selectivity is 62%.
(2) with after the catalyzer filtered and recycled after having reacted in (1), by (1) described operation repeated experiments, product is analyzed, as shown in table 4, cyclohexane conversion is 54%, and the hexanodioic acid selectivity is 63%; Use the catalyzer that reclaims repeatedly, the 3rd time the round-robin cyclohexane conversion is 52%, and the hexanodioic acid selectivity is 62%, and the 4th round-robin cyclohexane conversion is 52%, and the hexanodioic acid selectivity is 62%.Illustrate that employed multi-walled carbon nano-tubes catalyzer can be recycled in the technology of the present invention, this helps reducing production costs.
The recycling of table 4 multi-walled carbon nano-tubes catalyzer
| Access times | 1 | 2 | 3 | 4 |
| Transformation efficiency | 53％ | 54％ | 52％ | 52％ |
| Selectivity | 62％ | 63％ | 64％ | 62％ |
Catalyst stability embodiment 2
(1) acetate of 237g hexanaphthene and respective amount, tertbutyl peroxide and graphite catalyst are joined in the airtight batch reactor and mix, form mixed suspension.Wherein, the weight ratio of acetate and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and catalyzer is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 40: 1.This suspension under agitation is heated to 125 ℃, and aerating oxygen reacted 8 hours to 1.5MPa, and the separation of product and analytical procedure are with embodiment 1, and cyclohexane conversion is 24%, and the hexanodioic acid selectivity is 40%;
(2) with after the catalyzer filtered and recycled after having reacted in (1), by (1) described operation repeated experiments, product is analyzed, as shown in table 5, cyclohexane conversion is 23%, and the hexanodioic acid selectivity is 39%; Use the catalyzer that reclaims repeatedly, the 3rd time the round-robin cyclohexane conversion is 23%, and the hexanodioic acid selectivity is 41%, and the 4th round-robin cyclohexane conversion is 22%, and the hexanodioic acid selectivity is 39%.Illustrate that employed graphite catalyst can be recycled in the technology of the present invention, this helps reducing production costs.
The recycling of table 5 graphite catalyst
| Access times | 1 | 2 | 3 | 4 |
| Transformation efficiency | 24％ | 23％ | 23％ | 22％ |
| Selectivity | 40％ | 39％ | 41％ | 39％ |
Claims (5)
1, a kind of method of directly producing adipic acid by cyclohexane catalytic oxidation is characterized in that comprising the steps:
(1), forms mixed suspension with hexanaphthene, solvent, initiator and carbon material catalyst mix; The weight ratio of described solvent, carbon material catalyzer, initiator and hexanaphthene is 0-99: 0.000125-0.1: 0.0005-1: 1; The organic solvent of described solvent for mixing with hexanaphthene; Described carbon material catalyzer is carbon nanotube, graphite or gac; Described initiator is selected from one or more in tertbutyl peroxide, butanone, hexalin, the pimelinketone;
(2) step (1) gained mixing suspension is warming up to 50-250 ℃, aerating oxygen or air are as oxygenant, and keep-uping pressure is 0.1-5MPa, reaction 0.1-20h;
(3) step (2) reaction mixture is separated, obtain hexanodioic acid.
2,, it is characterized in that described carbon nanotube is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes according to the method for the described directly producing adipic acid by cyclohexane catalytic oxidation of claim 1.
3, according to the method for the described directly producing adipic acid by cyclohexane catalytic oxidation of claim 1, the weight ratio that it is characterized in that described carbon material catalyzer and hexanaphthene is 0.00167-0.005: 1.
4, according to the method for the described directly producing adipic acid by cyclohexane catalytic oxidation of claim 1, the temperature of reaction that it is characterized in that described step (2) is 100-200 ℃.
5,, it is characterized in that the described organic solvent that can mix with hexanaphthene is acetone, methyl alcohol, acetonitrile or acetate according to the method for the described directly producing adipic acid by cyclohexane catalytic oxidation of claim 1.
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| CN101337878B (en) * | 2008-08-13 | 2011-04-06 | 华南理工大学 | Method for directly producing adipic acid by cyclohexane catalytic oxidation |
| CN102001931A (en) * | 2010-10-19 | 2011-04-06 | 华南理工大学 | Method for preparing adipate |
| CN102040504A (en) * | 2010-10-29 | 2011-05-04 | 华南理工大学 | Method for preparing adipic acid by taking carbon nanotube filled with magnetic iron particles as catalyst |
| GB2480914A (en) * | 2010-05-28 | 2011-12-07 | Univ Texas | Carbocatalysts for chemical transformations |
| CN102816054A (en) * | 2012-08-30 | 2012-12-12 | 浙江大学 | Environment-friendly method for preparing adipic acid by catalytic oxidation |
| CN103193616A (en) * | 2013-04-02 | 2013-07-10 | 复旦大学 | Method for preparing adipic acid by oxidizing cyclohexene with air under catalysis of non-metal carbon |
| CN108855087A (en) * | 2017-05-12 | 2018-11-23 | 中国石油天然气股份有限公司 | Catalyst for preparing adipic acid, preparation method of catalyst and preparation method of adipic acid |
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| CN101337878B (en) * | 2008-08-13 | 2011-04-06 | 华南理工大学 | Method for directly producing adipic acid by cyclohexane catalytic oxidation |
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| GB2480914A (en) * | 2010-05-28 | 2011-12-07 | Univ Texas | Carbocatalysts for chemical transformations |
| GB2480914B (en) * | 2010-05-28 | 2013-08-21 | Univ Texas | Carbocatalysts for chemical transformations |
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| CN102001931B (en) * | 2010-10-19 | 2014-04-02 | 华南理工大学 | Method for preparing adipate |
| CN102040504A (en) * | 2010-10-29 | 2011-05-04 | 华南理工大学 | Method for preparing adipic acid by taking carbon nanotube filled with magnetic iron particles as catalyst |
| CN102040504B (en) * | 2010-10-29 | 2013-04-10 | 华南理工大学 | Method for preparing adipic acid by taking carbon nanotube filled with magnetic iron particles as catalyst |
| CN102816054A (en) * | 2012-08-30 | 2012-12-12 | 浙江大学 | Environment-friendly method for preparing adipic acid by catalytic oxidation |
| CN103193616A (en) * | 2013-04-02 | 2013-07-10 | 复旦大学 | Method for preparing adipic acid by oxidizing cyclohexene with air under catalysis of non-metal carbon |
| CN108855087A (en) * | 2017-05-12 | 2018-11-23 | 中国石油天然气股份有限公司 | Catalyst for preparing adipic acid, preparation method of catalyst and preparation method of adipic acid |
| CN110538670A (en) * | 2018-05-28 | 2019-12-06 | 中国石油化工股份有限公司 | Catalytic oxidation catalyst, preparation method thereof and cyclohexane oxidation method |
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| CN111097405A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Process for catalytic oxidation of cyclic hydrocarbons |
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| CN111097405B (en) * | 2018-10-29 | 2023-01-13 | 中国石油化工股份有限公司 | Process for catalytic oxidation of cyclic hydrocarbons |
| CN111229196A (en) * | 2018-11-29 | 2020-06-05 | 中国石油化工股份有限公司 | Catalyst, process for producing the same, and process for catalytic oxidation of hydrocarbons |
| CN111229196B (en) * | 2018-11-29 | 2022-09-27 | 中国石油化工股份有限公司 | Catalyst, process for producing the same, and process for catalytic oxidation of hydrocarbons |
| CN112569929A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Nano carbon-based material and preparation method thereof and catalytic oxidation method of cycloparaffin |
| CN112569929B (en) * | 2019-09-30 | 2023-05-05 | 中国石油化工股份有限公司 | Nanocarbon-based material, method for preparing same, and catalytic oxidation method for cycloalkane |
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