CN108114730A - Molybdenum-vanadium-tellurium-niobium catalytic agent composition - Google Patents
Molybdenum-vanadium-tellurium-niobium catalytic agent composition Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C07C2527/057—Selenium or tellurium; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
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Abstract
The present invention discloses molybdenum-vanadium-tellurium-niobium catalytic agent composition, and the mixture that said composition is made of molybdenum-vanadium-tellurium-niobium catalytic agent and stabilizer, the stabilizer is SiO2Or its mixture for being formed with SiC according to arbitrary proportion.The present invention creatively introduces the stabilizer with catalysis stabilization on the basis of previous work, can be under severe reaction conditions by catalyst stabilization, and significantly reduces the production cost of catalyst.
Description
Technical field
The present invention relates to the catalyst in reaction more particularly to the reaction that ethylene is prepared with ethane oxidation.
Background technology
Petrochemical field, the production technology route of ethylene are always one of hot spot of research staff's concern.Introduce oxidant (such as
O2Or Air etc.) ethylene dehydrogenation reaction is made to become a simple exothermic reaction by strong endothermic reaction, into numerous scientific research personnel's
One of thinking.According to document [Chem.Week, 137 (4), 36,1985] report, which can reduce by 20%~30%.So
And deep oxidation product CO is supported on the process thermodynamics2With the generation of CO, in this way, how to improve the selectivity of ethylene into
Most crucial technical barrier.Early in 1981, United States Patent (USP) US4250346 was disclosed for the Mo- in TOTAL OXIDATION REACTION OF ETHANE
V-Nb-O catalyst, ethylene selectivity is up to 90%, but the conversion ratio of ethane is no more than 10%.The United States Patent (USP) of nineteen eighty-three
US44100752 by V-P-O catalyst in TOTAL OXIDATION REACTION OF ETHANE, ethane conversion 52.53%, but ethylene selectivity compared with
It is low, it is only 43.16%；At ethylene selectivity higher (76.58%), ethane conversion is but very low, is only 4.13%.Canada
The 4th kind of element sb is introduced in patent CA122910358, is Mo-V-Sb-Nb-O catalyst, it is anti-to use it for ethane oxidation
Should, at 375 DEG C, ethane conversion 38%, ethylene selectivity 78%, conversion ratio, which has, to be obviously improved.Chinese patent
CN1069907 discloses a kind of fluoride as ethane oxidation catalyst for making ethylene, can be reacted under very high air speed, but
It needs to use substantial amounts of N in unstripped gas2As diluent (N2:O2:C2H6=85:5:10), main reaction result is：Work as reaction
Air speed 18000h-1During with 470 DEG C of reaction temperature, ethane conversion 37.2%, ethylene selectivity 95.9%；Work as reaction velocity
12000h-1During with 490 DEG C of reaction temperature, ethane conversion 59.1%, ethylene selectivity 84.7%.Similarly,
The fluoride catalysts that CN1120470 is provided then need higher reaction temperature (640 DEG C and 640 DEG C), and ethane conversion is higher,
80.82% is reached as high as, but regrettably, ethylene selectivity is unsatisfactory, is 70.0%~80.0%, the service life of catalyst is about
For 100h.Catalyst disclosed in CN1172790 is Na2WO4-Mn2O3/-S (S SiO2、TiO2Or MgO), which is used for second
Alkoxide is ethylene reaction produced, ethane conversion 69.8%, ethylene selectivity 76.5%, but needs to carry out at a high temperature of 750 DEG C,
In this way, lose reduces energy consumption and the meaning of equipment investment to a certain extent by exothermic reaction.And EP0544372 then uses one
As ethane oxidation catalyst for making ethylene, reaction temperature is also higher, is 470 DEG C for kind of heteropoly acid, although selectively higher (90%),
But conversion ratio is very low (being no more than 10%), and at such high reaction temperatures, the structural stability of such catalyst is one
A problem.When retrieving the related journals document of ethylene, it has been found that Mo-V-Nb-O catalyst is used for very early
In TOTAL OXIDATION REACTION OF ETHANE, primary product is acetic acid and ethylene (J.Catal.52,116 (1978)), later, in document
(Appl.Catal.70,129(1991)、Catal.Lett.19,17(1993)、J.Catal.175,16(1998)、
J.Catal.175,27 (1998)) in obtained comparing and go deep into systematic research, on the whole, such catalyst is often ethylene
With the coproduction of acetic acid, ethylene will not be produced, and the conversion ratio of ethane often (is typically not greater than than relatively low single selective
20%).Later, M.Roussel et al. (Appl.Catal.A:General, 308,62 (2006)) and Nb is replaced with Pd, and it is right
Compared between the two in TOTAL OXIDATION REACTION OF ETHANE as a result, but on the whole, the conversion ratio of ethane is still than relatively low.Cause such
Metal oxide catalyst performance varies widely, as document (Chem.Commu., 1906 (2002),
J.Catal.225,228 (2004), J.Catal.252,271 (2007), Catal.Today, 142,272 (2009),
Catal.Commu.,22(2012)、Appl.Catal.A:Gen., 433-424,41 (2012)) as report, introduce the
Four kinds of element T e can obtain ethylene (more than 90% in partial catalyst) with high selectivity, while ethane conversion is very high (logical
Often not less than 35%).Under given conditions, partial catalyst (Chem.Commu., 1906 (2002)) obtains second at 400 DEG C
The yield of alkene is 71.5% (ethane conversion 88.5%, ethylene selectivity 80.8%), before having good commercial Application
Scape.It is well known that a catalyst will have good prospects for commercial application, it is necessary to have good stability, and urge
Agent price itself should not be too high.We do not find related Mo-V-Te-Nb-O catalyst in ethane oxidation system from document
Stability information in ethylene reaction.According to the result of study of our early stages, Mo-V-Te-Nb-O catalyst is in ethane oxidation system
It is more stable in itself under mild reaction condition in ethylene reaction, and relatively acutely (such as high-speed is high when reaction condition
Temperature pressurization etc.) in the case of, it is likely that since the drastically rise of hot(test)-spot temperature causes catalyst performance to be gradually reduced, reason can
Can be precipitated since the Te in active component is easier to be reduced when hot(test)-spot temperature is higher, and then cause catalyst
The change of composition and structure, and finally affect performance of the catalyst in TOTAL OXIDATION REACTION OF ETHANE.It is urged therefore it provides one kind has
The catalyst or catalyst prod for the property changed just seem especially significant.
The content of the invention
The purpose of the present invention, which first consists in, provides a kind of molybdenum-vanadium-tellurium-niobium catalytic agent composition, and said composition is by molybdenum vanadium tellurium niobium
The mixture of catalyst and stabilizer composition, the stabilizer is SiO2Or its mixing for being formed with SiC according to arbitrary proportion
Object.
In the technical solution of above-mentioned catalyst combination, SiO is such as used2The stabilizer of-SiC binary, then preferably make stabilizer
The mass percentage of middle SiC is 0~60%.
In the molybdenum-vanadium-tellurium-niobium catalytic agent composition of the present invention, the mass percentage shared by the stabilizer is no more than
95%, preferably 30~70%, more preferable 30~50%.
The present invention above-mentioned carbon monoxide-olefin polymeric in, the molybdenum-vanadium-tellurium-niobium catalytic agent can be according to CN1795987A,
What the method for CN101612564 obtained.In the present invention, the molybdenum-vanadium-tellurium-niobium catalytic agent in the composition has general formula
Mo1.0VxTeyNbzOn, wherein, x is that 0.2~1.0, y is the valence state that 0.2~1.0, z is 0.1~0.5, n and Mo, V, Te and Nb
And content is related.
It includes the following steps more specifically, can be prepared by hydrothermal synthesis method：
(1) mixed reaction solution of ammonium molybdate, vanadic sulfate, telluric acid, niobium oxalate is placed in stainless steel cauldron, from room temperature
160~230 DEG C are warming up to 2~10 DEG C/min of heating rate, when heat preservation 2-20 is small, is then down to room temperature naturally.
(2) reaction product is taken out after aging, filters, is dry, products therefrom is handled using two-segment calcining：First segment is in sky
When roasting 1~3 is small at 150~300 DEG C in gas, molybdenum vanadium tellurium is made when 400~700 DEG C of roastings 1~5 are small in nitrogen in second segment
Niobium catalytic powder.
Further, on the basis of obtained molybdenum-vanadium-tellurium-niobium catalytic agent powder, composition of the present invention is by molybdenum vanadium tellurium
Niobium catalytic powder is mixed with stabilizer by one of following methods：
A. interior mixed method：It grinds and is molded after catalyst powder is mixed with stabilizer；
B. outer mixed method：It is mixed again with stabilizer after catalyst powder is first molded.
On the other hand, the present invention provides the preparation method of above-mentioned molybdenum-vanadium-tellurium-niobium catalytic agent composition, includes the following steps：
(1) mixed reaction solution of ammonium molybdate, vanadic sulfate, telluric acid, niobium oxalate is placed in stainless steel cauldron, from room temperature
160~230 DEG C are warming up to 2~10 DEG C/min of heating rate, when heat preservation 2~20 is small, is then down to room temperature naturally；
(2) reaction product is taken out after aging, filters, is dry, products therefrom is handled using two-segment calcining：First segment is in sky
When roasting 1~3 is small at 150~300 DEG C in gas, molybdenum vanadium tellurium is made when 400~700 DEG C of roastings 1~5 are small in nitrogen in second segment
Niobium catalytic powder；
(3) the molybdenum-vanadium-tellurium-niobium catalytic agent powder prepared by step (2) is mixed with stabilizer by one of following methods：
A. interior mixed method：It grinds and is molded after catalyst powder is mixed with stabilizer；
B. outer mixed method：It is mixed again with stabilizer after catalyst powder is first molded.
It is aoxidized instead in ethane to ethylene in another aspect, the present invention provides the carbon monoxide-olefin polymeric for oxidation reaction
Application in answering.
Include suitable for the more specific ethane to ethylene oxidation reaction condition of the oxidation reaction of above application：Reaction temperature
300~450 DEG C, 0.5~15amt of reaction pressure are spent, reacts total air speed 1000h-1~50000h-1.It preferably includes：Reaction temperature
It is 1~10amt for 340~400 DEG C, reaction pressure, reacts total air speed for 2000h-1~8000h-1。
The present invention creatively introduces the diluent with catalysis stabilization on the basis of previous work.Stabilizer
Introducing have of both significance：First, it can be under severe reaction conditions by catalyst stabilization, this is because stablizing
Agent is conducive to the scattered of reaction heat and transfers, so as to which catalytic inner be avoided to generate higher hot(test)-spot temperature；Secondth, stabilizer sheet
Body can also significantly reduce the production cost of catalyst as a kind of cheap diluent.
Specific embodiment
In ethane selective oxidation is ethylene reaction produced, reaction product is divided into air-liquid two-phase.Gas-phase product includes CO, CO2With
C2H4, liquid product is mainly minimal amount of acetic acid.
Conversion ratio, selectivity and yield are calculated according to the following formula：
Conversion ratio (%)=(∑ Mi × ni)/[2 × (amount of the substance of ethane in charging)] × 100%
Selectivity (%)=(Mi × ni)/(∑ Mi × ni) × 100%
Yield (%)=conversion ratio × selectivity × 100
In above-mentioned formula, Mi：The amount of the substance of certain product i；ni：Institute's carbon atom quantity in certain product i molecules.
Without specified otherwise, it is heretofore described and the mild reaction conditions of ethane Selective Oxidation be：Reaction temperature
350 DEG C, react total volume space velocity 1500h-1, ethane/oxygen/nitrogen (volume ratio) is 30/20/50, reaction pressure 1atm
(normal pressure)；Harsh reaction condition is：380 DEG C of reaction temperature reacts total volume space velocity 4000h-1, ethane/oxygen/nitrogen (body
Product ratio) it is 30/20/50, reaction pressure is 3atm (3 atmospheric pressure).
In the present invention, when addressing the additive amount of stabilizer, used percentages represent added stabilizer
The shared mass percentage in entire carbon monoxide-olefin polymeric.For example, " it is with the addition of 30% Alpha-Al when addressing2O3”
When, refer in the carbon monoxide-olefin polymeric finally obtained, stabilizer Alpha-Al2O3Mass percentage be 30%.
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
Mo-V-Te-Nb-O catalyst (catalytic active components are prepared using temperature programming hydrothermal synthesis method
(CN101612564), step includes：Ammonium molybdate, vanadic sulfate, telluric acid and the niobium oxalate for weighing proportioning first are dissolved in heat respectively
In deionized water, each self-heating slowly successively mixed each solution after 30 minutes, continued stirring after ten minutes by it
It is transferred in stainless steel tube synthesis reactor, rises to 190 DEG C from room temperature with 10 DEG C/min of heating rate, room is down to naturally after keeping the temperature 20h
Temperature is then taken out, and filters, dry.The grinding of obtained black solid is placed in calcination vessel, with 3 DEG C/min of heating
Rate from room temperature be raised to 300 DEG C and keep the temperature 2 it is small when after (atmosphere is air), then with same heating rate rise to 600 DEG C after
(atmosphere is nitrogen) Temperature fall after when continuation of insurance temperature 2 is small, products therefrom are the Mo-V-Te-Nb-O catalyst after roasting, finally
Molding granulation is sieved into the catalyst granules that grain size is 20~30 mesh and is used for evaluating catalyst.
Taking 20~30 mesh catalyst of 1g, reaction condition is for ethane Selective Oxidation：350 DEG C of reaction temperature, reaction
Total volume space velocity 1500h-1, ethane/oxygen/nitrogen (volume ratio) is 30/20/50, and reaction pressure is 1atm (normal pressure).Reaction
Continue 900 it is small when, reaction result is listed in Table 1 below.The result shows that catalyst performance is highly stable under the conditions of comparatively gentle.
Table 1
Embodiment 2
Mo-V-Te-Nb-O catalyst is prepared according to the method for embodiment 1.
The Mo-V-Te-Nb-O catalyst prepared by 20~30 mesh of 1g is taken for ethane Selective Oxidation, reaction condition
Different from embodiment 1, specific reaction condition is：380 DEG C of reaction temperature reacts total volume space velocity 4000h-1, ethane/oxygen/
Nitrogen (volume ratio) is 30/20/50, and reaction pressure is 3atm (3 atmospheric pressure).Reaction continue 900 it is small when, reaction result is listed in
In table 2.The result shows that under more violent reaction condition, catalyst activity declines substantially at any time, the interior second when 900 is small
Alkane conversion ratio declines about 26.8%.
Table 2
Embodiment 3
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 30% Alpha-Al in addition in preparation process2O3,
The Mo-V-Te-Nb-O carbon monoxide-olefin polymerics of the present embodiment are made.
The carbon monoxide-olefin polymeric of the above-mentioned preparation of 20~30 mesh of 1g is taken to be used for ethane Selective Oxidation, reaction condition and reality
It is identical to apply example 2.Reaction continue 900 it is small when, reaction result is listed in Table 3 below.The result shows that Al2O3Be added be beneficial to it is stably catalyzed
Agent performance activity component, even if reaction condition is harsher, when 900 is small, interior ethane conversion declines about 15.6%, hence it is evident that suppression
The decrease speed for having delayed catalyst performance in other words is made.
Table 3
Embodiment 4
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 30% SiO in addition in preparation process2, this reality is made
Apply the Mo-V-Te-Nb-O carbon monoxide-olefin polymerics of example.
20~30 mesh catalyst of 1g is taken to be used for ethane Selective Oxidation, reaction condition is same as Example 2.Reaction is held
It is continuous 900 it is small when, reaction result is listed in Table 4 below.The result shows that SiO2The basicly stable catalyst activity component of addition, 900
Ethane conversion only declines 2.4% in hour, hence it is evident that inhibits the decrease speed for having delayed catalyst performance in other words.And it urges
Change stabilization and be substantially better than Al2O3(embodiment 3).
Table 4
Embodiment 5
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 25% SiC's and 25% in addition in preparation process
SiO2, the Mo-V-Te-Nb-O carbon monoxide-olefin polymerics of obtained the present embodiment.
20~30 mesh catalyst of 1g is taken to be used for ethane Selective Oxidation, reaction condition is same as Example 2.Reaction is held
It is continuous 900 it is small when, reaction result is listed in Table 5 below.
Table 5
Embodiment 6
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 30% SiO in addition in preparation process2, this reality is made
Apply the Mo-V-Te-Nb-O carbon monoxide-olefin polymerics of example.
20~30 mesh catalyst of 1g is taken to be used for ethane Selective Oxidation, reaction condition is same as Example 1.Reaction is held
It is continuous 900 it is small when, reaction result is listed in Table 6 below.The result shows that under mild reaction condition, SiO2Addition to catalyst live
Property component property only plays the role of diluent, interior ethane conversion is without decline when 900 is small without influence.
Table 6
Embodiment 7
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 50% SiC's and 45% in addition in preparation process
SiO2, the Mo-V-Te-Nb-O carbon monoxide-olefin polymerics of obtained the present embodiment.
20~30 mesh catalyst of 1g is taken to be used for ethane Selective Oxidation, reaction condition is same as Example 2.Reaction is held
It is continuous 900 it is small when, reaction result is shown in Table 12.The result shows that same as Example 7,50% SiC and 45% SiO2It is mixed
Incorporation complete stability catalyst activity component is closed, interior ethane conversion is almost unchanged when 900 is small.
Table 12
Claims (10)
1. molybdenum-vanadium-tellurium-niobium catalytic agent composition, which is characterized in that said composition is made of molybdenum-vanadium-tellurium-niobium catalytic agent and stabilizer
Mixture, the stabilizer is SiO2Or its mixture for being formed with SiC according to arbitrary proportion.
2. composition according to claim 1, which is characterized in that the mass percentage of SiC is 0 in the stabilizer
~60%.
3. composition according to claim 1, which is characterized in that the mass percentage of stabilizer is not in the composition
More than 95%.
4. composition according to claim 1, which is characterized in that molybdenum-vanadium-tellurium-niobium catalytic agent has general formula in the composition
Mo1.0VxTeyNbzOn, wherein, x is that 0.2~1.0, y is the valence state that 0.2~1.0, z is 0.1~0.5, n and Mo, V, Te and Nb
And content is related.
5. composition according to claim 1, which is characterized in that the molybdenum-vanadium-tellurium-niobium catalytic agent passes through hydrothermal synthesis method
It prepares, includes the following steps：
(1) mixed reaction solution of ammonium molybdate, vanadic sulfate, telluric acid, niobium oxalate is placed in stainless steel cauldron, from room temperature with 2
~10 DEG C/min of heating rate is warming up to 160~230 DEG C, when heat preservation 2-20 is small, is then down to room temperature naturally；
(2) reaction product is taken out after aging, filters, is dry, products therefrom is handled using two-segment calcining：First segment is in air
At 150~300 DEG C roasting 1~3 it is small when, second segment in nitrogen 400~700 DEG C roasting 1~5 it is small when, be made molybdenum vanadium tellurium niobium urge
Agent powder.
6. composition according to claim 5, which is characterized in that the composition is by molybdenum-vanadium-tellurium-niobium catalytic agent powder and surely
Determine agent to be mixed by one of following methods：
A. interior mixed method：It grinds and is molded after catalyst powder is mixed with stabilizer；
B. outer mixed method：It is mixed again with stabilizer after catalyst powder is first molded.
7. the preparation method of molybdenum-vanadium-tellurium-niobium catalytic agent composition described in claim 1, includes the following steps：
(1) mixed reaction solution of ammonium molybdate, vanadic sulfate, telluric acid, niobium oxalate is placed in stainless steel cauldron, from room temperature with 2
~10 DEG C/min of heating rate is warming up to 160~230 DEG C, when heat preservation 2~20 is small, is then down to room temperature naturally；
(2) reaction product is taken out after aging, filters, is dry, products therefrom is handled using two-segment calcining：First segment is in air
At 150~300 DEG C roasting 1~3 it is small when, second segment in nitrogen 400~700 DEG C roasting 1~5 it is small when, be made molybdenum vanadium tellurium niobium urge
Agent powder；
(3) the molybdenum-vanadium-tellurium-niobium catalytic agent powder prepared by step (2) is mixed with stabilizer by one of following methods：
A. interior mixed method：It grinds and is molded after catalyst powder is mixed with stabilizer；
B. outer mixed method：It is mixed again with stabilizer after catalyst powder is first molded.
8. application of the molybdenum-vanadium-tellurium-niobium catalytic agent composition described in claim 1 in ethane to ethylene oxidation reaction.
9. application according to claim 8, which is characterized in that the ethane to ethylene oxidation reaction condition includes：Instead
300~450 DEG C of temperature, 0.5~15amt of reaction pressure are answered, reacts total air speed 1000h-1~50000h-1。
10. application according to claim 9, which is characterized in that the ethane to ethylene oxidation reaction condition includes：Instead
It answers that temperature is 340~400 DEG C, reaction pressure is 1~10amt, reacts total air speed for 2000h-1~8000h-1。
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Cited By (4)
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| CN110256186A (en) * | 2019-06-19 | 2019-09-20 | 惠生工程（中国）有限公司 | A kind of method of low-carbon alkanes oxidative dehydrogenation alkene |
| CN111892473A (en) * | 2019-05-06 | 2020-11-06 | 惠生工程（中国）有限公司 | Method and system for producing ethylene from low-carbon hydrocarbon through oxidative dehydrogenation |
| CN111892472A (en) * | 2019-05-06 | 2020-11-06 | 惠生工程（中国）有限公司 | Method and system for preparing ethylene by catalytic oxidative dehydrogenation of low-carbon hydrocarbon |
| CN116328805A (en) * | 2021-12-15 | 2023-06-27 | 中国科学院大连化学物理研究所 | Catalyst for low-carbon alkane selective oxidation of high-value chemicals and preparation method thereof |
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| CN116328805A (en) * | 2021-12-15 | 2023-06-27 | 中国科学院大连化学物理研究所 | Catalyst for low-carbon alkane selective oxidation of high-value chemicals and preparation method thereof |
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