CN108114733A - Molybdenum vanadium tellurium niobium composite catalyst - Google Patents
Molybdenum vanadium tellurium niobium composite catalyst Download PDFInfo
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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention discloses a kind of molybdenum vanadium tellurium niobium composite catalyst, which is made of molybdenum-vanadium-tellurium-niobium catalytic agent and stabilizer, and the stabilizer is SiC.The present invention creatively introduces the SiC 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
Ethylene is the base stock of petrochemical industry, is the pillar industries of the national economy, and has 75% petrochemical industry production at present
Product are by ethylene production；Ethylene yield has become the important symbol for weighing a national oil chemical engineering industry level.By 2015
Bottom, the annual capacity of China's ethylene is 21,190,000 tons, and yield is up to 19,990,000 tons.Ethylene is main at present or is existed by including ethane
Interior steam heat scission reaction carries out industrial production, which usually requires 800~1100 DEG C of high temperature strong endothermic reaction, therefore
There are the following problems for the process：1st, high energy consumption.According to related document (A Proceeding of the 8th Ethylene
Producer Conference:AIChE, New York) report, the energy consumption of the process is up to 18.5MJ/kg-C2H4, and into one
It is very big to walk the difficulty reduced.2nd, product composition is complicated.Cracking reaction is complicated radical reaction, the product species of generation compared with
More, on the one hand can reduce the selectivity (ethylene is usually no more than 80%) of ethylene reduces raw material availability, on the other hand also can
The separating difficulty for increasing product (particularly generates low-boiling H2And methane).3rd, regular carbon remover is needed.Pyroreaction causes
Tube wall meeting carbon distribution, need to stop regular carbon remover, certainly will so influence production efficiency.4th, equipment investment is high.Since pyroreaction needs
The alloy pyrolysis furnace reactor of special substance is wanted, so equipment investment is higher.Therefore, develop low energy consumption, it is more environmentally-friendly
Ethylene route, into relation ethylene industry develop pressing issues.
Undoubtedly, oxidant (such as O is introduced2Or Air etc.) ethylene dehydrogenation reaction is made to become one simply by strong endothermic reaction
Exothermic reaction, into one of thinking of numerous scientific research personnel.According to document [Chem.Week, 137 (4), 36,1985] report, the mistake
Journey energy consumption can reduce by 20%~30%.However, deep oxidation product CO is supported on the process thermodynamics2With the generation of CO, in this way,
How the selectivity of ethylene is improved into most crucial technical barrier.Early in 1981, United States Patent (USP) US4250346 was disclosed
For the Mo-V-Nb-O catalyst in TOTAL OXIDATION REACTION OF ETHANE, ethylene selectivity is up to 90%, but the conversion ratio of ethane is no more than
10%.The United States Patent (USP) US44100752 of nineteen eighty-three is by V-P-O catalyst in TOTAL OXIDATION REACTION OF ETHANE, ethane conversion to be
52.53%, but ethylene selectivity is relatively low, is only 43.16%；At ethylene selectivity higher (76.58%), ethane conversion is but
It is very low, it is only 4.13%.The 4th kind of element sb is introduced in Canadian Patent CA122910358, is that Mo-V-Sb-Nb-O is urged
Agent uses it for TOTAL OXIDATION REACTION OF ETHANE, and at 375 DEG C, ethane conversion 38%, ethylene selectivity 78%, conversion ratio has
It is obviously improved.Chinese patent CN1069907 discloses a kind of fluoride as ethane oxidation catalyst for making ethylene, can be very high
It is reacted under air speed, but needs to use substantial amounts of N in unstripped gas2As diluent (N2:O2:C2H6=85:5:10) it is, main
Reaction result is：As reaction velocity 18000h-1During with 470 DEG C of reaction temperature, ethane conversion 37.2%, ethylene selectivity
95.9%；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), second
Alkane conversion ratio is higher, reaches as high as 80.82%, but regrettably, ethylene selectivity is unsatisfactory, is 70.0%~80.0%,
The service life of catalyst is about 100h.Catalyst disclosed in CN1172790 is Na2WO4-Mn2O3/-S (S SiO2、TiO2Or MgO),
The catalyst is ethylene reaction produced for ethane oxidation, ethane conversion 69.8%, ethylene selectivity 76.5%, but needs 750
It is carried out at a high temperature of 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 a kind of heteropoly acid, and reaction temperature is also higher as ethane oxidation catalyst for making ethylene, is 470 DEG C, although
Selectivity higher (90%), but conversion ratio is very low (being no more than 10%), and at such high reaction temperatures, such catalyst
Structural stability be a problem.When retrieving the related journals document of ethylene, it has been found that Mo-V-Nb-O
For catalyst very early in TOTAL OXIDATION REACTION OF ETHANE, primary product is acetic acid and ethylene (J.Catal.52,116 (1978)), after
Come, 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 past
Toward the coproduction for being ethylene and acetic acid, ethylene will not be produced single selective, and the conversion ratio of ethane often than it is relatively low (usually not
More than 20%).Later, M.Roussel et al. (Appl.Catal.A:General, 308,62 (2006)) and Nb is replaced with Pd,
And 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 composite catalyst, and the composite catalyst is by molybdenum vanadium tellurium niobium
Catalyst is formed with stabilizer, and the stabilizer is SiC.
In the molybdenum vanadium tellurium niobium molybdenum vanadium tellurium niobium composite catalyst of the present invention, the mass percentage shared by the stabilizer is not
More than 95%, preferably 5~95%, more preferable 30~70%.
In the above-mentioned molybdenum vanadium tellurium niobium composite catalyst of the present invention, the molybdenum-vanadium-tellurium-niobium catalytic agent can be basis
What the method for CN1795987A, CN101612564 obtained.In the present invention, the molybdenum-vanadium-tellurium-niobium catalytic agent 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, composite catalyst of the present invention is by molybdenum
Vanadium-tellurium-niobium catalytic agent 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 composite catalyst, 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.
In another aspect, molybdenum vanadium tellurium niobium composite catalyst is used in ethane to ethylene oxidation reaction described in present invention offer
Application.
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% SiC in addition in preparation process, 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.It can be seen that the addition complete stability catalyst activity component of SiC, the interior second when 900 is small
Alkane conversion ratio is almost unchanged.
Table 4
Embodiment 5
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 5% SiC in addition in preparation process, this implementation is made
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 5 below.The addition of a small amount of SiC can stabilizing catalyst activity component, the interior second when 900 is small
Alkane conversion ratio only declines 0.7%.
Table 5
Embodiment 6
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 50% SiC in addition in preparation process, 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 6 below.The result shows that the addition complete stability catalyst activity component of 50%SiC,
900 interior ethane conversions when small are almost unchanged.
Table 6
Embodiment 7
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 70% SiC in addition in preparation process, 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 shown in Table 7.The result shows that the incorporation complete stability catalyst activity component of 70%SiC,
900 interior ethane conversions when small are almost unchanged.
Table 7
Embodiment 8
With reference to embodiment 1 preparation method, and in preparation process within mix method be with the addition of 50% SiC, be made this reality
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 8 below.The result shows that the hybrid mode of stabilizer and catalyst activity component does not change
SiC is to the stablizing effect of catalyst activity component.
Table 8
Embodiment 9
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
Al2O3, 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 9 below.The experimental results showed that compared with only adding the embodiment data of SiC, mixing is mixed
Effect when the mode effect entered is not as good as only SiC.
Table 9
Embodiment 11
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 30% SiC in addition in preparation process, 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 shown in Table 11.The result shows that under mild reaction condition, the addition of SiC lives to catalyst
Property component property only plays the role of diluent, interior ethane conversion is without decline when 900 is small without influence.
Table 11
Embodiment 12
With reference to the preparation method of embodiment 1, and mixed method is with the addition of 95% SiC in addition in preparation process, 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 shown in Table 12.The result shows that same as Example 7, the incorporation complete stability catalysis of 95%SiC
Agent active component, when 900 is small, interior ethane conversion is almost unchanged.
Table 12
Claims (10)
1. molybdenum vanadium tellurium niobium composite catalyst, which is characterized in that the composite catalyst is made of molybdenum-vanadium-tellurium-niobium catalytic agent and stabilizer,
The stabilizer is SiC.
2. molybdenum vanadium tellurium niobium composite catalyst according to claim 1, which is characterized in that stabilizer in the composite catalyst
Mass percentage be no more than 95%.
3. molybdenum vanadium tellurium niobium composite catalyst according to claim 2, which is characterized in that stabilizer in the composite catalyst
Mass percentage be 5%~95%.
4. molybdenum vanadium tellurium niobium composite catalyst according to claim 1, which is characterized in that the molybdenum-vanadium-tellurium-niobium catalytic agent tool
There is formula M o1.0VxTeyNbzOn, wherein, x is that 0.2~1.0, y is that 0.2~1.0, z is 0.1~0.5, n and Mo, V, Te and Nb
Valence state and content it is related.
5. molybdenum vanadium tellurium niobium composite catalyst according to claim 1, which is characterized in that the molybdenum-vanadium-tellurium-niobium catalytic agent leads to
Hydrothermal synthesis method preparation is crossed, is included 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. molybdenum vanadium tellurium niobium composite catalyst according to claim 5, which is characterized in that the composite catalyst 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.
7. the preparation method of molybdenum vanadium tellurium niobium composite catalyst 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 composite catalyst 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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| 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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