CN106582607A - Catalyst for dehydrogenation of isobutane - Google Patents
Catalyst for dehydrogenation of isobutane Download PDFInfo
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- CN106582607A CN106582607A CN201510673375.9A CN201510673375A CN106582607A CN 106582607 A CN106582607 A CN 106582607A CN 201510673375 A CN201510673375 A CN 201510673375A CN 106582607 A CN106582607 A CN 106582607A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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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
- C07C5/3335—Catalytic processes with metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/20—Vanadium, niobium or tantalum
- C07C2523/22—Vanadium
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Abstract
The invention relates to a catalyst for dehydrogenation of isobutane, a preparation method and application, and mainly solves the problem of low conversion rate of the catalyst in the prior art. The catalyst is a catalyst for the preparation of isobutene by the adoption of dehydrogenation of isobutane. The catalyst comprises carriers, active constituents and assistants. According to the technical scheme, at least one of the SiO2, Al2O3 and ZnO are adopted as carriers for the catalyst, the active constituents are vanadium, and one or several rare earth metals are selected as the assistants. The catalyst for dehydrogenation of isobutane well solves the problem of the low conversion rate of the catalyst, and can be used in the industrial production of isobutene by the dehydrogenation of isobutane under a CO2 atmosphere.
Description
Technical field
The present invention relates to a kind of dehydrogenation of isobutane catalyst, preparation method and applications.
Background technology
Isobutene. is a kind of very important industrial chemicals, in Chemical Manufacture, the purposes of isobutene. widely,
Can be used to synthesizing methyl tertbutyl ether (MTBE), ethyl tert-butyl oxide (ETBE), butyl rubber, ABS
Resin etc..With the production-scale expansion of isobutene. downstream product, the demand of isobutene. also constantly increases.
The isobutene. amount that traditional method is obtained can not meet the demand in market.In addition, the C4 resources of China are very rich
Richness, but compared with American-European countries China C4 resource utilizations than relatively low less than 40%, only American-European countries
Half or so, and be concentrated mainly in the utilization of alkene, most alkane is used as fuel, brings greatly money
Source wastes.The isobutene. that the dehydrogenation of isobutane of relative low price produces high added value can be solved into isobutene.
Shortage can produce bigger economic benefit again.
Preparing isobutene through dehydrogenation of iso-butane is broadly divided into catalytic dehydrogenation, dioxygen oxidation dehydrogenation and carbon dioxide atmosphere dehydrogenation
Three kinds of methods.Catalytic dehydrogenation of isobutane has realized at present industrialization, but the reaction is limited by thermodynamical equilibrium,
And observable index is larger.The dehydrogenation of iso-butane dioxygen oxidation can bring deep oxidation, and products distribution is uncontrolled, causes
The low problem of selectivity.Preparing isobutene through dehydrogenation of iso-butane combines catalytic dehydrogenation and oxygen oxygen under carbon dioxide atmosphere
The advantage of fluidized dehydrogenation, is a kind of new method with potential competition ability.Carbon dioxide can be with dehydrogenation generation
There is inverse water gas reaction in hydrogen, limit so as to break thermodynamical equilibrium, dehydrogenation reaction is moved to product；Or
Person's carbon dioxide directly can occur oxidative dehydrogenation with iso-butane.Above two mechanism can improve isobutyl
The equilibrium conversion of alkane.Additionally, carbon dioxide is changed into during the course of the reaction more as main greenhouse gases
For active and be industrially easier the carbon monoxide for utilizing, greenhouse emissions not only reduced but also have taken full advantage of carbon money
Source, with certain social value.
Carbon dioxide atmosphere preparing isobutene through dehydrogenation of iso-butane is extensively taken seriously, and for example, Shimada et al. is adopted
With activated carbon supported ferric oxide catalyst, reaction temperature is that the conversion ratio of iso-butane under the conditions of 600 DEG C is about
23%, selectivity is about 80%, and catalyst inactivation is fast, and iso-butane conversion ratio is down to 13% after reacting 3 hours
(Applied Catalysis A:General, 1998 volume 168 page 243～250).Ogonowski seminars
VMgO catalyst is used, when reaction temperature is 600 DEG C, conversion ratio is 13%, selectivity is 80% (Catalysis
Communications, 2009 volume 11 page 132～136).It is prepared by Chinese patent CN 102631914A
Mesoporous carbon for carrier vanadium pentoxide catalyst, under the conditions of reaction temperature the is 610 DEG C conversion of iso-butane
Rate is about 32%, and selectivity is about 91.4%.In terms of comprehensive, develop high conversion rate, olefine selective it is high and into
This cheap catalyst is still crucial.
The content of the invention
One of the technical problem to be solved is that catalyst iso-butane conversion ratio is relatively low in prior art
A kind of problem, there is provided catalyst of new preparing isobutene through dehydrogenation of iso-butane.There are the catalyst higher olefins to select
The characteristics of property.
The two of the technical problem to be solved in the present invention be to provide it is a kind of with solve that one of technical problem is corresponding to urge
Agent preparation method.
The three of the technical problem to be solved in the present invention are to provide a kind of answering for the catalyst of one of solution technical problem
With.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：The catalysis of dehydrogenation of isobutane
Agent, including carrier, active component and auxiliary agent, described catalyst with SiO2, Al2O3 and ZnO at least
One kind be carrier, with vanadium as active component, with rare earth metal one or more as auxiliary agent.
In above-mentioned technical proposal, described rare earth metal is not particularly limited, such as but not limited to heavy rare earth metal
Y, Yb, Ho, Er etc. in element.But it is preferred that the rare earth includes Y and Yb simultaneously, now turn in isobutene.
Both rate aspects have synergism.
In above-mentioned technical proposal, the weight/mass percentage composition of vanadium is preferably 0.5～30% in terms of V2O5, more preferably
2～15%.
In above-mentioned technical proposal, the weight/mass percentage composition of auxiliary agent is preferably 0.2 in terms of the trivalent of rare earth～
4.5%.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：One of above-mentioned technical problem
Technical scheme described in catalyst preparation method, comprise the following steps：
1) aequum carrier is successively mixed with the solution containing vanadium and the solution containing auxiliary agent, or by aequum carrier
Mix with the solution simultaneously containing vanadium and containing auxiliary agent；
2) roasting obtains the catalyst.
In above-mentioned technical proposal, described solution preferably adopts the solvent of water, one skilled in the art will appreciate that root
According to vanadium-containing compound and the property containing auxiliary compound, pH is adjusted so that above-claimed cpd is dissolved in acid or alkali
Solution is formed in water.
Carrier can successively mix with the solution containing vanadium and the solution containing auxiliary agent, and sequencing is not limited, or
Mix with the mixed solution simultaneously containing vanadium and containing auxiliary agent.
Using carrier with containing vanadium and during solution hybrid mode containing auxiliary agent, the preparation method of mixed solution can be but
It is not limited to：
A, the compound dissolution of the desired amount of vanadium is carried out in water with appropriate oxalic acid aqueous solution in beaker it is molten
Solution, obtains the aqueous solution containing vanadium；
B, by the desired amount of rare earth compound add step a in aqueous solution containing vanadium in, stirring and dissolving must contain
The aqueous solution of vanadium and auxiliary agent；
In above-mentioned technical proposal, the compound of vanadium is not particularly limited, such as but not limited to ammonium metavanadate, sulphuric acid
One kind of vanadyl and vanadyl oxalate, the rare earth compound it is not also specifically limited, such as but not limited to nitrate,
Chlorate etc..
In above-mentioned technical proposal, sintering temperature is preferably 550～750 DEG C, more preferably 600～700 DEG C.
In above-mentioned technical proposal, roasting time is preferably 2～10 hours, more preferably 4～6 hours.
In above-mentioned technical proposal, one skilled in the art will appreciate that being preferably step 1) and step 2) between
With dry step.
In above-mentioned technical proposal, dry temperature is preferably 85～145 DEG C.
In above-mentioned technical proposal, 24～36 hours are preferably drying time.
To solve the three of above-mentioned technical problem, the technical solution used in the present invention is as follows：Above-mentioned catalyst is applied to
Under carbon dioxide atmosphere in the reaction of preparing isobutene through dehydrogenation of iso-butane.
In above-mentioned technical proposal, preferably carbon dioxide is 1～10 with the mol ratio of iso-butane.
In above-mentioned technical proposal, the temperature of reaction is preferably 550～650 DEG C.
In above-mentioned technical proposal, the mass space velocity of iso-butane 0.2～2 hour -1.
Iso-butane conversion ratio, selective isobutene are calculated as follows：
The present invention also has higher under the experiment condition of the present invention, while the conversion ratio of iso-butane keeps higher
Selective isobutene, achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated：
Specific embodiment
【Embodiment 1】
1st, catalyst preparation
The ammonium metavanadate and the Yttrium trinitrate equivalent to 2 grams of Y2O3 that will be equivalent to 10 grams of V2O5 is dissolved in 25 millis
In rising the oxalic acid aqueous solution of 0.25 mol/L, mix with 88 grams of SiO2 carriers, stand 4 hours at room temperature,
Then at 120 DEG C of dryings 28 hours, catalyst needed for roasting is obtained for 6 hours most in 600 DEG C of muffle furnaces was
It is easy to compare, the composition of catalyst is listed in into table 1.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 6.0, reaction temperature is 580 DEG C, and the mass space velocity of iso-butane is 0.5 hour -1, and reaction pressure is normal pressure.
For ease of comparing, catalyst activity evaluation the results are shown in Table 2.
【Comparative example 1】
1st, catalyst preparation
The ammonium metavanadate that will be equivalent to 12 grams of V2O5 is dissolved in the oxalic acid aqueous solution of 25 milliliter of 0.25 mol/L
In, mix with 88 grams of SiO2 carriers, at room temperature 4 hours are stood, then at 120 DEG C of dryings 28 hours,
Catalyst needed for roasting is obtained for 6 hours most in 600 DEG C of muffle furnaces, for ease of comparing, by the group of catalyst
In column in table 1.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 6.0, reaction temperature is 580 DEG C, and the mass space velocity of iso-butane is 0.5 hour -1, and reaction pressure is normal pressure.
For ease of comparing, catalyst activity evaluation the results are shown in Table 2.
【Comparative example 2】
1st, catalyst preparation
The Yttrium trinitrate that will be equivalent to 12 grams of Y2O3 is dissolved in the oxalic acid aqueous solution of 25 milliliter of 0.25 mol/L,
Mix with 88 grams of SiO2 carriers, stand 4 hours at room temperature, then at 120 DEG C of dryings 28 hours, finally
Catalyst needed for roasting is obtained for 6 hours in 600 DEG C of muffle furnaces, for ease of comparing, the composition of catalyst is arranged
In table 1.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 6.0, reaction temperature is 580 DEG C, and the mass space velocity of iso-butane is 0.5 hour -1, and reaction pressure is normal pressure.
For ease of comparing, catalyst activity evaluation the results are shown in Table 2.
【Embodiment 2】
1st, catalyst preparation
The ammonium metavanadate and the Ytterbium(III) nitrate. equivalent to 2 grams of Yb2O3 that will be equivalent to 10 grams of V2O5 is dissolved in 25 millis
In rising the oxalic acid aqueous solution of 0.25 mol/L, mix with 88 grams of SiO2 carriers, stand 4 hours at room temperature,
Then at 120 DEG C of dryings 28 hours, catalyst needed for roasting is obtained for 6 hours most in 600 DEG C of muffle furnaces was
It is easy to compare, the composition of catalyst is listed in into table 1.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 6.0, reaction temperature is 580 DEG C, and the mass space velocity of iso-butane is 0.5 hour -1, and reaction pressure is normal pressure.
For ease of comparing, catalyst activity evaluation the results are shown in Table 2.
【Embodiment 3】
1st, catalyst preparation
Will be equivalent to the ammonium metavanadate of 10 grams of V2O5, the Yttrium trinitrate equivalent to 1 gram of Y2O3 and equivalent to 1 gram
The Ytterbium(III) nitrate. of Yb2O3 is dissolved in the oxalic acid aqueous solution of 25 milliliter of 0.25 mol/L, with 88 grams of SiO2 carriers
Mixing, stands 4 hours at room temperature, then at 120 DEG C of dryings 28 hours, roasts most in 600 DEG C of muffle furnaces
Catalyst needed for being obtained for 6 hours is burnt, for ease of comparing, the composition of catalyst table 1 is listed in into.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 6.0, reaction temperature is 580 DEG C, and the mass space velocity of iso-butane is 0.5 hour -1, and reaction pressure is normal pressure.
For ease of comparing, catalyst activity evaluation the results are shown in Table 2.
As a result show, Y and Yb has synergism in terms of catalyst activity and selectivity is improved.
【Embodiment 4】
1st, catalyst preparation
The ammonium metavanadate and the holmium nitrate equivalent to 2 grams of Ho2O3 that will be equivalent to 10 grams of V2O5 is dissolved in 25
In the oxalic acid aqueous solution of 0.25 mol/L of milliliter, mix with 8 grams of SiO2 carriers, stand 4 hours at room temperature,
Then at 120 DEG C of dryings 28 hours, catalyst needed for roasting is obtained for 6 hours most in 600 DEG C of muffle furnaces was
It is easy to compare, the composition of catalyst is listed in into table 1.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 6.0, reaction temperature is 580 DEG C, and the mass space velocity of iso-butane is 0.5 hour -1, and reaction pressure is normal pressure.
For ease of comparing, catalyst activity evaluation the results are shown in Table 2.
【Embodiment 5】
1st, catalyst preparation
The ammonium metavanadate and the Erbium trinitrate equivalent to 2 grams of Er 2O3 that will be equivalent to 10 grams of V2O5 is dissolved in 25
In the oxalic acid aqueous solution of 0.25 mol/L of milliliter, mix with 88 grams of SiO2 carriers, 4 are stood at room temperature little
When, then at 100 DEG C of dryings 24 hours, catalyst needed for roasting is obtained for 4 hours most in 600 DEG C of muffle furnaces,
For ease of comparing, the composition of catalyst is listed in into table 1.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 5.0, reaction temperature is 590 DEG C, and the mass space velocity of iso-butane is 1.0 hours -1, and reaction pressure is normal pressure.
For ease of comparing, catalyst activity evaluation the results are shown in Table 2.
【Embodiment 6】
1st, catalyst preparation
The ammonium metavanadate and the Yttrium trinitrate equivalent to 0.5 gram of Y2O3 that will be equivalent to 30 grams of V2O5 is dissolved in 45
In the oxalic acid aqueous solution of 0.25 mol/L of milliliter, mix with 69.5 grams of Al2O3 carriers, 4 are stood at room temperature
Hour, then at 80 DEG C of dryings 36 hours, catalysis needed for roasting is obtained for 2 hours most in 800 DEG C of muffle furnaces
Agent.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 1.0, reaction temperature is 650 DEG C, and the mass space velocity of iso-butane is 0.5 hour -1, and reaction pressure is normal pressure.
Reaction result is：Iso-butane conversion ratio is 35.9%, and selective isobutene is 87.2%.
【Embodiment 7】
1st, catalyst preparation
The ammonium metavanadate and the Yttrium trinitrate equivalent to 4.5 grams of Y2O3 that will be equivalent to 1 gram of V2O5 is dissolved in 25 millis
In rising the oxalic acid aqueous solution of 0.25 mol/L, mix with 94.5 grams of ZnO carriers, stand 4 hours at room temperature,
Then at 150 DEG C of dryings 24 hours, catalyst needed for roasting is obtained for 10 hours most in 550 DEG C of muffle furnaces.
2nd, evaluating catalyst
As stated above obtained catalyst carries out activity rating in fixed bed reactors, and process is as follows：
The internal diameter of reactor is 8 millimeters of stainless steel tube, long 400 millimeters.Carbon dioxide and iso-butane mol ratio
For 10.0, reaction temperature is 560 DEG C, and the mass space velocity of iso-butane is 0.5 hour -1, and reaction pressure is normal pressure.
Reaction result is：Iso-butane conversion ratio is 18.5%, and selective isobutene is 92.6%.
Table 1
| V2O5 | Y2O3 | Yb2O3 | Ho2O3 | Er2O3 | Carrier | |
| Embodiment 1 | 10 | 2 | - | - | - | 88 |
| Comparative example 1 | 12 | - | - | - | - | 88 |
| Comparative example 2 | - | 12 | - | - | - | 88 |
| Embodiment 2 | 10 | - | 2 | - | - | 88 |
| Embodiment 3 | 10 | 1 | 1 | - | - | 88 |
| Embodiment 4 | 7 | - | - | 2 | - | 88 |
| Embodiment 5 | 7 | - | - | - | 2 | 88 |
Note：Catalyst composition is represented with weight percentage in table 1.
Table 2
| Iso-butane conversion ratio/% | Selective isobutene/% | |
| Embodiment 1 | 38.6 | 91.7 |
| Comparative example 1 | 19.5 | 89.1 |
| Comparative example 2 | 10.8 | 94.9 |
| Embodiment 2 | 34.2 | 92.3 |
| Embodiment 3 | 45.7 | 91.2 |
| Embodiment 4 | 30.7 | 92.1 |
| Embodiment 5 | 31.4 | 91.9 |
Claims (10)
1. the catalyst of dehydrogenation of isobutane, including carrier, active component and auxiliary agent, it is characterised in that：Described urges
Agent is with SiO2、Al2O3It is carrier with least one in ZnO, with vanadium as active component, with rare earth metal
One or more be auxiliary agent.
2. catalyst according to claim 1, it is characterised in that the weight/mass percentage composition of vanadium is with V2O5It is calculated as
0.5～30%.
3. catalyst according to claim 1, it is characterised in that the weight/mass percentage composition of auxiliary agent is with the trivalent of rare earth
Oxide is calculated as 0.2～4.0%.
4. the preparation method of the catalyst described in claim 1, comprises the following steps：
1) aequum carrier is successively mixed with the solution containing vanadium and the solution containing auxiliary agent, or by aequum carrier with it is same
When containing vanadium and containing auxiliary agent solution mixing；
2) roasting obtains the catalyst.
5. preparation method according to claim 4, it is characterised in that sintering temperature is 550～750 DEG C.
6. preparation method according to claim 4, it is characterised in that when roasting time is roasting in 2～10 hours
Between.
7. preparation method according to claim 4, it is characterised in that step 1) and step 2) between have
Dry step.
8. preparation method according to claim 7, it is characterised in that dry temperature is 85～145 DEG C.
9. preparation method according to claim 7, it is characterised in that drying time is 24～36 hours.
10. the catalyst described in claim 1 is applied to the reaction of preparing isobutene through dehydrogenation of iso-butane under carbon dioxide atmosphere
In.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020049462A1 (en) * | 2018-09-05 | 2020-03-12 | Sabic Global Technologies B.V. | Vanadium oxide supported catalyst for alkane dehydrogenation |
| CN113908823A (en) * | 2020-07-10 | 2022-01-11 | 中国石油天然气股份有限公司 | Vanadium-based catalyst and preparation method thereof |
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| CN101165031A (en) * | 2006-10-16 | 2008-04-23 | 罗门哈斯公司 | Integrated catalytic process for converting alkanes to alkenes and catalysts useful for same |
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| WO2020049462A1 (en) * | 2018-09-05 | 2020-03-12 | Sabic Global Technologies B.V. | Vanadium oxide supported catalyst for alkane dehydrogenation |
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| CN113908823A (en) * | 2020-07-10 | 2022-01-11 | 中国石油天然气股份有限公司 | Vanadium-based catalyst and preparation method thereof |
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