CN116020505A - Catalyst for hydrocarbon selective oxidation and preparation method and application thereof - Google Patents
Catalyst for hydrocarbon selective oxidation and preparation method and application thereof Download PDFInfo
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- CN116020505A CN116020505A CN202111243331.4A CN202111243331A CN116020505A CN 116020505 A CN116020505 A CN 116020505A CN 202111243331 A CN202111243331 A CN 202111243331A CN 116020505 A CN116020505 A CN 116020505A
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
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- 239000012018 catalyst precursor Substances 0.000 claims abstract description 21
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000011812 mixed powder Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
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- 239000002245 particle Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
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- 238000007873 sieving Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
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- 238000007493 shaping process Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 abstract description 9
- 239000010439 graphite Substances 0.000 abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011733 molybdenum Substances 0.000 abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 8
- 239000002278 tabletting lubricant Substances 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 31
- 238000012216 screening Methods 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 20
- 239000001273 butane Substances 0.000 description 19
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 19
- 239000001569 carbon dioxide Substances 0.000 description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
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- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000005078 molybdenum compound Substances 0.000 description 3
- 150000002752 molybdenum compounds Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Catalysts (AREA)
Abstract
The invention relates to a catalyst for hydrocarbon selective oxidation, a preparation method and application thereof. The catalyst comprises an active phase and an auxiliary phase, wherein the general formula of the active phase is V 1 P x Mo y C z O u The method comprises the steps of carrying out a first treatment on the surface of the The auxiliary phase comprises molybdenum disulfide. The preparation method comprises the following steps: s1, reacting a reaction system containing a vanadium source, a phosphorus source and a solvent to obtain a post-reaction system; s2, carrying out solid-liquid separation treatment on the reacted system to obtain precursor powder; s3, mixing the precursor powder with molybdenum disulfide to obtain mixed powder; s4, carrying out molding treatment on the mixed powder to obtain a catalyst precursor; s5, activating the catalyst precursor to obtain the catalyst. The molybdenum disulfide is used for replacing graphite when the catalyst is preparedAs a tabletting lubricant, excessive carbon is prevented from being introduced, and the added molybdenum disulfide can be used as the tabletting lubricant and can be effectively introduced into a molybdenum auxiliary agent.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a catalyst for hydrocarbon selective oxidation, a preparation method and application thereof.
Background
The gas phase selective oxidation of hydrocarbons is an important catalytic reaction, and can be used for preparing various oxidation products such as organic anhydride compounds and the like. One of the typical products is maleic anhydride (maleic anhydride).
Maleic anhydride, also known as Maleic Anhydride (MA), is a commonly used important organic chemical raw material, and the third largest anhydride species is consumed worldwide. Maleic anhydride is currently used mainly in the production of unsaturated polyester resins, alkyd resins, 1, 4-Butanediol (BDO), gamma-butyrolactone (GBL), and Tetrahydrofuran (THF) chemicals. In addition, it is widely used in various fine chemical fields. In particular, with the current banning of plastic, there is an increasing demand for degradable plastics, and as one of the important raw materials for degradable plastics, there is also a need for maleic anhydride to be rapidly increased in the future.
The production of maleic anhydride is mainly divided into two types, and benzene is adopted as a production raw material in the earliest production method, but the proportion of the production process of the benzene method in the production of maleic anhydride is increasingly reduced due to the harm of the raw material and the environment and the influence of economic factors; the main stream production method of maleic anhydride adopts normal butane as production raw material, including fixed bed, fluidized bed and moving bed, and the processes are characterized by that they have practical industrial application, but they share a common point that these processes for preparing maleic anhydride by oxidizing normal butane all adopt the same kind of catalyst, i.e. Vanadium Phosphorus Oxide (VPO) catalyst.
Through many years of research, VPO catalysts have been consideredThe catalyst system most effective for catalyzing vapor phase hydrocarbons, particularly n-butane, to produce maleic anhydride has heretofore been employed. Commercial VPO catalysts typically employ an organic phase to produce a precursor, which is calcined to activate and shaped by adding a shaping lubricant (typically graphite) to form the final catalyst. Earlier studies found that the carbon content of the catalyst had an important effect on the performance of the VPO catalyst (CN 1152746C). It can be seen that the addition of the shaped lubricant graphite has a significant impact on the catalyst performance. The addition of excessive graphite may even cause catalyst activation and runaway during the reaction, resulting in rapid catalyst deactivation and reduced selectivity. Molybdenum is used as a co-catalytic element for oxidation reaction, which can modulate the oxidation-reduction capability of the catalyst, reduce the formation of inactive phase and play a very key role in the performance of the catalyst. The traditional adding mode of the molybdenum auxiliary agent in the vanadium phosphorus oxide catalyst is that the molybdenum auxiliary agent (CN 112705233A and CN 112495410A) is introduced by adding molybdenum precursors such as ammonium molybdate or phosphomolybdic acid in the process of preparing precursor powder by an organic phase method. It is worth noting that molybdenum disulfide (MoS 2 ) As a representative molybdenum-containing compound, a graphite-like material, in which Mo atomic layers are sandwiched between two layers of closely packed S atoms in adjacent molybdenum disulfide crystals, a layered structure in the form of S-Mo-S is formed, wherein strong covalent bonds are present between Mo-S and mainly Van der Waals forces are present between S layers, which makes it a highly effective solid lubricant useful for forming pressed sheets of electrode materials, catalysts and the like.
The inventors found that if MoS can be used in the formation of the vanadium phosphorus oxide catalyst 2 The solid lubricant can replace graphite as a tabletting lubricant on one hand, avoid the introduction of excessive carbon, and can effectively introduce Mo auxiliary agent through the mode on the other hand, thereby being expected to improve the performance of maleic anhydride catalyst prepared by n-butane oxidation.
Disclosure of Invention
In order to overcome the problems in the prior art, the inventor of the present invention has conducted extensive and intensive studies to provide a catalyst for selective oxidation of hydrocarbons, and a preparation method and application thereof. For example, it is an object of the present invention to provide a catalyst for hydrocarbon selective oxidation, which can realize the introduction of a molybdenum additive and obtain a molded hydrocarbon selective oxidation catalyst with a high yield, while ensuring the catalytic strength.
In order to achieve the above object, the first aspect of the present invention provides a catalyst for the selective oxidation of hydrocarbons, comprising an active phase and an auxiliary phase. Wherein the general formula of the active phase is shown as formula (I):
V 1 P x Mo y C z O u formula (I)
In the formula (I), the value of x is in the range of 0.5-2, the value of y is in the range of 0.01-0.1, the value of z is in the range of 0-0.02, and u is the number of oxygen atoms meeting the valence of the active phase.
According to the present invention, x is preferably in the range of 0.95 to 1.6.
According to the present invention, the catalyst may be referred to as a vanadium phosphorus oxide catalyst.
According to the present invention, the XRD diffraction pattern of the catalyst, analyzed by X-ray diffraction, has diffraction peaks ascribed to molybdenum compounds at angles of 2θ of 14.4.+ -. 0.3, 32.7.+ -. 0.3, 35.9.+ -. 0.3 and 39.5.+ -. 0.3.
According to the invention, the molybdenum compound is mainly molybdenum disulfide.
In some embodiments of the invention, the mass percent of the active phase in the catalyst is 90% to 99.5% based on the total weight of the catalyst; the mass percentage of the auxiliary agent phase is 0.5% -5%.
In some embodiments of the invention, the mass percent of carbon element in the catalyst is no greater than 5%.
According to the invention, the carbon element is neither an active phase nor an auxiliary phase in the present invention.
According to the invention, the carbon element is introduced into the catalyst during the preparation process by the raw material containing C, the solvent or the gas in the atmosphere in which the reaction is carried out.
In some embodiments of the invention, the compressive strength of the catalyst is 15N to 30N.
According to the invention, a ZQJ-II intelligent particle strength tester of Dalian intelligent testing machine factory is adopted, and the test standard method is based on the application of ZQJ intelligent particle strength tester of China Petroleum and chemical industry Standard and quality (pages 31-33,28 in 3 rd 1991), so as to obtain the compressive strength of the catalyst.
According to a second aspect of the present invention there is provided a method of preparing a catalyst according to the first aspect of the present invention comprising the steps of:
s1, reacting a reaction system containing a vanadium source, a phosphorus source and a solvent to obtain a post-reaction system;
s2, carrying out solid-liquid separation treatment on the reacted system to obtain precursor powder;
s3, mixing the precursor powder with molybdenum disulfide to obtain mixed powder;
s4, carrying out molding treatment on the mixed powder to obtain a catalyst precursor;
s5, activating the catalyst precursor to obtain the catalyst.
In some embodiments of the present invention, in step S1, the vanadium source is selected from at least one of vanadium pentoxide, ammonium metavanadate and vanadium organic acid, preferably vanadium pentoxide.
In some embodiments of the invention, the phosphorus source is phosphoric acid, preferably 85 to 110wt% phosphoric acid, more preferably 95 to 105wt% phosphoric acid.
In some embodiments of the invention, the solvent is selected from at least one of monohydric and polyhydric alcohols, preferably a mixture of isobutanol and benzyl alcohol, preferably in a molar ratio of 2:1 to 6:1. In the reaction system, the mole ratio of vanadium element to phosphorus element is (0.6-1.1): 1. In the reaction system, the ratio of the total mass of the solvent to the total mass of the vanadium source is (5-10): 1.
In some embodiments of the invention, in step S1, the reaction conditions include: the temperature is 100-120 ℃.
The pressure of the reaction is not particularly limited in the present invention, and the reaction of step S1 is preferably carried out at normal pressure.
According to the present invention, in step S1, the reaction system containing the vanadium source, the phosphorus source and the solvent may be mixed and then heated and refluxed for 2 to 20 hours.
According to the invention, the solvent may also function as a reducing agent. If the solvent to be added does not function as a reducing agent, a reducing agent may be added additionally, and the type of reducing agent to be selected is not particularly limited, and those ordinarily used in the art can be used by those skilled in the art.
In some embodiments of the present invention, in step S2, the solid-liquid separation treatment may be performed by filtration, evaporation, or the like, for example, the post-reaction system obtained in step S1 is filtered and washed with a solvent (a solution of at least one of the same components contained in the solvent of step S1), and the resulting cake may be dried at 120 ℃ for 16 hours.
In some embodiments of the invention, in step S3, the molybdenum disulfide is added in an amount of 0.5% to 5%, preferably 1% to 3% of the mass of the precursor powder.
According to the invention, in step S3, the molybdenum disulfide has a purity of greater than 95%.
In some embodiments of the present invention, in step S4, the forming process includes sequentially performing a first tabletting process on the precursor powder using a powder tabletting machine under a pressure of 10 to 40MPa, and then performing a crushing, sieving and a second tabletting process, and preferably, the sieving includes sieving out catalyst particles having a particle size of 20 to 160 meshes and performing a subsequent second tabletting process, so as to obtain a hollow cylindrical catalyst to be activated having a height of 4 to 6 mm.
According to the invention, in step S4, the sieved 20-160 mesh catalyst particles may be placed on a rotary tablet press for a second tabletting process.
The method and conditions for the crushing are not particularly limited in the present invention, and a person skilled in the art can select an appropriate process according to the target product.
In some embodiments of the present invention, in step S5, the activation treatment is performed under an atmosphere formed of one or more of an oxygen-containing gas, an inert gas, and water vapor; preferably, the inert gas is at least one of nitrogen, helium and argon.
According to the present invention, in step S5, the catalyst precursor may be subjected to an activation treatment three times under an atmosphere formed of one or more of an oxygen-containing gas, an inert gas, and water vapor.
According to the invention, in step S5, the activation treatment is performed three times, and the activation treatment is performed for 2-5 hours in the air atmosphere at 200-350 ℃ for the first time; performing activation treatment for 2-5 h at 300-450 ℃ in an atmosphere with 15-25% of air, 15-25% of nitrogen, 5-15% of carbon dioxide and 45-55% of water vapor in volume content for the second time; and thirdly, performing activation treatment for 2-5 h at 400-450 ℃ in an atmosphere of 35-45% of nitrogen, 5-15% of carbon dioxide and 45-55% of water vapor by volume.
In some embodiments of the invention, the method for preparing the catalyst comprises the steps of:
1) Mixing a vanadium compound, phosphoric acid and an organic solvent serving as a reducing agent and a solvent, and heating and refluxing for 2-20 hours to obtain a solution after reaction;
2) Filtering the solution after the reaction and washing the solution with the same organic solvent as in the step 1), and then carrying out heat treatment on a filter cake at 100-120 ℃ to obtain precursor powder;
3) Uniformly mixing precursor powder and molybdenum disulfide, and performing pre-granulation and secondary tabletting treatment to obtain a hollow cylindrical catalyst to be activated, wherein the height of the hollow cylindrical catalyst to be activated is 4-6 mm;
4) And (3) activating the hollow cylindrical catalyst to be activated in an atmosphere consisting of oxygen-containing gas, inert gas and water vapor to obtain the catalyst.
According to a third aspect of the invention, there is provided the use of a catalyst according to the first aspect of the invention and/or a catalyst prepared by the method according to the second aspect of the invention in the selective oxidation of hydrocarbons, in particular in the catalytic oxidation of n-butane to maleic anhydride.
In some embodiments of the present invention, the catalyst is used for preparing maleic anhydride by gas-phase catalytic oxidation using n-butane as raw material, and comprises: the catalyst is placed in a fixed bed reactor, the reaction atmosphere comprises n-butane with the molar concentration of 1% -1.7%, maleic anhydride is produced through thermocatalysis, and the reaction process conditions comprise: space velocity of 1000-3000hr -1 The reaction temperature is 300-500 ℃, and the reaction pressure is normal pressure.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1) The auxiliary agent phase of the catalyst provided by the invention is molybdenum disulfide, and the catalyst contains less carbon elements;
2) According to the preparation method of the catalyst, molybdenum disulfide is adopted to replace graphite to be used as a tabletting forming lubricant, so that excessive graphite carbon is prevented from being introduced;
3) According to the preparation method of the catalyst, the added molybdenum disulfide can be used as a tabletting lubricant and can be effectively introduced with a molybdenum auxiliary agent;
4) When the catalyst provided by the invention is applied to preparing maleic anhydride by catalytic oxidation of n-butane, the butane conversion rate is high, the maleic anhydride selectivity is high, and the yield is high.
Drawings
The invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 shows the XRD spectrum of the catalyst prepared in example 1 of the present invention;
figure 2 shows the XRD spectrum of the catalyst prepared according to comparative example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents or equipment used are not identified to the manufacturer and are conventional products available commercially or prepared according to the preparation methods disclosed in the prior art.
In the examples, the butane conversion was calculated by:
butane conversion (%) =molar amount of n-butane consumed by reaction/molar amount of n-butane fed to the feedstock x 100%.
In the examples, the maleic anhydride selectivity was calculated by:
maleic anhydride selectivity (%) = molar amount of maleic anhydride produced/molar amount of n-butane consumed by reaction x 100%.
Example 1
1. Preparation of the catalyst
250g of vanadium pentoxide is added to a mixed solution of 2500ml of isobutanol and 1000ml of benzyl alcohol, stirring is started, about 300g of 100wt.% phosphoric acid is slowly added, the mixed solution is heated to 110 ℃, reflux is carried out for 16 hours, after heating is stopped, the mixed solution is filtered and washed with isobutanol, and the obtained filter cake is dried for 16 hours at 120 ℃ to obtain precursor powder. And screening the precursor powder to obtain precursor powder smaller than 200 meshes, and fully and uniformly mixing 5g of molybdenum disulfide compound with 250g of precursor powder smaller than 200 meshes to form mixed powder. Tabletting the mixture under the pressure of 20MPa, crushing, screening, taking a part with 20-160 meshes after screening, transferring the pre-granulated particles to a rotary tabletting machine, carrying out rotary tabletting on the catalyst structure with the height of 5mm to obtain a catalyst precursor. The catalyst precursor is roasted for 3 hours at 250 ℃ in an air atmosphere, then is roasted for 3 hours at the temperature of 425 ℃ in an atmosphere of 20% of air, 20% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio, and finally is roasted for 3 hours at 450 ℃ in an atmosphere of 40% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio to obtain a catalyst product A1.
The catalyst product A1 was subjected to strength analysis, and the compressive strength was found to be 23N.
The result of the X-ray diffraction analysis of the catalyst product A1 is shown in FIG. 1. As can be seen from fig. 1, there are major diffraction characteristic peaks at 2θ=12.5, 14.4, 18.5, 22.8, 28.4, 29.3, 29.9, 32.7, 35.9, 39.5, 43.2 and 49.8, wherein the peaks of 2θ=14.4, 32.7, 35.9 and 39.5 are attributed to the diffraction peaks of the molybdenum compound.
2. Catalytic reaction
The catalyst product A1 obtained was fed with 1.5vol% butane for 2000hr -1 Butane conversion was determined to be 85.8% and maleic anhydride selectivity to 63.1% as assessed in a fixed bed reactor at space velocity.
Example 2
1. Preparation of the catalyst
250g of vanadium pentoxide is added into a mixed solution of 2500ml of isobutanol and 800ml of benzyl alcohol, stirring is started, about 350g of 110wt.% phosphoric acid is slowly added, the mixed solution is heated to 110 ℃, reflux is carried out for 16 hours, after heating is stopped, the mixed solution is filtered and washed by isobutanol, and the obtained filter cake is dried for 16 hours at 120 ℃ to obtain precursor powder. And screening the precursor powder to obtain precursor powder smaller than 200 meshes, and fully and uniformly mixing 5g of molybdenum disulfide compound with 250g of precursor powder smaller than 200 meshes to form mixed powder. Tabletting the mixture under the pressure of 20MPa, crushing, screening, taking a part with 20-160 meshes after screening, transferring the pre-granulated particles to a rotary tabletting machine, carrying out rotary tabletting on the catalyst structure with the height of 5mm to obtain a catalyst precursor. The catalyst precursor is roasted for 3 hours at 250 ℃ in an air atmosphere, then is roasted for 3 hours at the temperature of 425 ℃ in an atmosphere of 20% of air, 20% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio, and finally is roasted for 3 hours at 450 ℃ in an atmosphere of 40% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio to obtain a catalyst product A2.
The catalyst product A2 was subjected to strength analysis, and the compressive strength was found to be 22N.
2. Catalytic reaction
The catalyst product A2 obtained was fed with 1.5vol% butane for 2000hr -1 Butane conversion was measured to be 84.9% and maleic anhydride selectivity 62.8% at space velocity as assessed in a fixed bed reactor.
Example 3
1. Preparation of the catalyst
250g of vanadium pentoxide is added to a mixed solution of 2500ml of isobutanol and 800ml of benzyl alcohol, stirring is started, about 320g of 110wt.% phosphoric acid is slowly added, the mixed solution is heated to 110 ℃, reflux is carried out for 16 hours, after heating is stopped, the mixed solution is filtered and washed with isobutanol, and the obtained filter cake is dried for 16 hours at 120 ℃ to obtain precursor powder. And screening the precursor powder to obtain precursor powder smaller than 200 meshes, and fully and uniformly mixing 10g of molybdenum disulfide compound with 250g of precursor powder smaller than 200 meshes to form mixed powder. Tabletting the mixture under the pressure of 20MPa, crushing, screening, taking a part with 20-160 meshes after screening, transferring the pre-granulated particles to a rotary tabletting machine, carrying out rotary tabletting on the catalyst structure with the height of 5mm to obtain a catalyst precursor. The catalyst precursor is roasted for 3 hours at 250 ℃ in an air atmosphere, then is roasted for 3 hours at the temperature of 425 ℃ in an atmosphere of 20% of air, 20% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio, and finally is roasted for 3 hours at 450 ℃ in an atmosphere of 40% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio to obtain a catalyst product A3.
The catalyst product A3 was subjected to strength analysis, and the compressive strength was found to be 24N.
2. Catalytic reaction
The catalyst product A3 obtained was fed with 1.5vol% butane for 2000hr -1 Butane conversion was estimated to be 85.9% and maleic anhydride selectivity to 62.1% in a fixed bed reactor at space velocity.
Example 4
1. Preparation of the catalyst
250g of vanadium pentoxide is added to a mixed solution of 2500ml of isobutanol and 800ml of benzyl alcohol, stirring is started, about 280g of 110wt.% phosphoric acid is slowly added, the mixed solution is heated to 110 ℃, reflux is carried out for 16 hours, after heating is stopped, the mixed solution is filtered and washed with isobutanol, and the obtained filter cake is dried for 16 hours at 120 ℃ to obtain precursor powder. And screening the precursor powder to obtain precursor powder smaller than 200 meshes, and fully and uniformly mixing 5g of molybdenum disulfide compound with 250g of precursor powder smaller than 200 meshes to form mixed powder. Tabletting the mixture under the pressure of 20MPa, crushing, screening, taking a part with 20-160 meshes after screening, transferring the pre-granulated particles to a rotary tabletting machine, carrying out rotary tabletting on the catalyst structure with the height of 5mm to obtain a catalyst precursor. The catalyst precursor is roasted for 3 hours at 250 ℃ in an air atmosphere, then is roasted for 3 hours at the temperature of 425 ℃ in an atmosphere of 20% of air, 20% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio, and finally is roasted for 3 hours at 450 ℃ in an atmosphere of 40% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio to obtain a catalyst product A4.
The catalyst product A4 was subjected to strength analysis, and the compressive strength was found to be 22N.
2. Catalytic reaction
The catalyst product A4 obtained was fed with 1.5vol% butane for 2000hr -1 Butane conversion was found to be 83.9% and maleic anhydride selectivity to 62.5% as assessed in a fixed bed reactor at space velocity.
Example 5
1. Preparation of the catalyst
250g of vanadium pentoxide is added to a mixed solution of 2500ml of isobutanol and 800ml of benzyl alcohol, stirring is started, about 300g of 110wt.% phosphoric acid is slowly added, the mixed solution is heated to 110 ℃, reflux is carried out for 16 hours, after heating is stopped, the mixed solution is filtered and washed with isobutanol, and the obtained filter cake is dried for 16 hours at 120 ℃ to obtain precursor powder. And screening the precursor powder to obtain precursor powder smaller than 200 meshes, and fully and uniformly mixing 2g of molybdenum disulfide compound with 250g of precursor powder smaller than 200 meshes to form mixed powder. Tabletting the mixture under the pressure of 20MPa, crushing, screening, taking a part with 20-160 meshes after screening, transferring the pre-granulated particles to a rotary tabletting machine, carrying out rotary tabletting on the catalyst structure with the height of 5mm to obtain a catalyst precursor. The catalyst precursor is roasted for 3 hours at 250 ℃ in an air atmosphere, then is roasted for 3 hours at the temperature of 425 ℃ in an atmosphere of 20% of air, 20% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio, and finally is roasted for 3 hours at 450 ℃ in an atmosphere of 40% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio to obtain a catalyst product A5.
The catalyst product A5 was subjected to strength analysis, and the compressive strength was found to be 18N.
2. Catalytic reaction
The catalyst product A5 obtained was fed with 1.5vol% butane for 2000hr -1 Butane conversion was found to be 83.4% and maleic anhydride selectivity to 62.1% as assessed in a fixed bed reactor at space velocity.
Example 6
1. Preparation of the catalyst
320g of ammonium metavanadate was added to a mixed solution of 2500ml of isobutanol and 1000ml of benzyl alcohol, stirring was started and about 300g of 100wt.% phosphoric acid was slowly added, the mixed solution was heated to 110℃and refluxed for 16 hours, after stopping heating, the mixed solution was filtered and washed with isobutanol, and the obtained filter cake was dried at 120℃for 16 hours to obtain a precursor powder. And screening the precursor powder to obtain precursor powder smaller than 200 meshes, and fully and uniformly mixing 5g of molybdenum disulfide compound with 250g of precursor powder smaller than 200 meshes to form mixed powder. Tabletting the mixture under the pressure of 20MPa, crushing, screening, taking a part with 20-160 meshes after screening, transferring the pre-granulated particles to a rotary tabletting machine, carrying out rotary tabletting on the catalyst structure with the height of 5mm to obtain a catalyst precursor. The catalyst precursor is roasted for 3 hours at 250 ℃ in an air atmosphere, then is roasted for 3 hours at the temperature of 425 ℃ in an atmosphere of 20% of air, 20% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio, and finally is roasted for 3 hours at 450 ℃ in an atmosphere of 40% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio to obtain a catalyst product A6.
The catalyst product A6 was subjected to strength analysis, and the compressive strength was found to be 22N.
2. Catalytic reaction
The resulting catalyst product A6 was evaluated in a fixed bed reactor at a butane feed rate of 1.5vol%, at a space velocity of 2000hr-1, and a butane conversion of 84.8% and a maleic anhydride selectivity of 62.0% was measured.
Example 7
1. Preparation of the catalyst
250g of vanadium pentoxide is added into a mixed solution of 2500ml of ethylene glycol and 1000ml of benzyl alcohol, stirring is started, about 300g of 100wt.% phosphoric acid is slowly added, the mixture is heated to reflux and then is subjected to reflux reaction for 16 hours, the mixed solution is filtered and washed by isobutanol after heating is stopped, and the obtained filter cake is dried at 120 ℃ for 16 hours to obtain precursor powder. And screening the precursor powder to obtain precursor powder smaller than 200 meshes, and fully and uniformly mixing 5g of molybdenum disulfide compound with 250g of precursor powder smaller than 200 meshes to form mixed powder. Tabletting the mixture under the pressure of 20MPa, crushing, screening, taking a part with 20-160 meshes after screening, transferring the pre-granulated particles to a rotary tabletting machine, carrying out rotary tabletting on the catalyst structure with the height of 5mm to obtain a catalyst precursor. The catalyst precursor is roasted for 3 hours at 250 ℃ in an air atmosphere, then is roasted for 3 hours at the temperature of 425 ℃ in an atmosphere of 20% of air, 20% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio, and finally is roasted for 3 hours at 450 ℃ in an atmosphere of 40% of nitrogen, 10% of carbon dioxide and 50% of water vapor by volume ratio to obtain a catalyst product A7.
The catalyst product A7 was subjected to an intensity analysis, and the intensity was found to be 21N.
2. Catalytic reaction
The resulting catalyst product A6 was evaluated in a fixed bed reactor at a butane feed of 1.5vol%, at a space velocity of 2000hr-1, and a butane conversion of 83.9% and a maleic anhydride selectivity of 61.1% was measured.
Comparative example 1
1. Preparation of the catalyst
Essentially the same as in example 1 except that 6g of graphite powder was used in place of 5g of the molybdenum disulfide compound in example 1, catalyst product B1 was produced.
The catalyst product B1 was subjected to strength analysis, and the compressive strength was found to be 25N.
The result of the X-ray diffraction analysis of the catalyst product B1 is shown in FIG. 2. As can be seen from fig. 2, there are main diffraction characteristic peaks at 2θ=12.5, 18.5, 22.8, 26.5, 28.4, 29.3, 29.9, 43.2 and 49.8, wherein the peak of 2θ=26.5 is ascribed to the diffraction peak of graphite carbon, and it can be found that the diffraction peak-to-peak intensity of carbon is larger in the catalyst product using graphite as a tabletting lubricant.
2. Catalytic reaction
The resulting catalyst product B1 was evaluated in a fixed bed reactor at a butane feed rate of 1.5vol%, at a space velocity of 2000hr-1, and a butane conversion of 84.8% and a maleic anhydride selectivity of 59.9% was measured.
It is noted that the above-described embodiments are only for explaining the present invention, and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (11)
1. A catalyst for the selective oxidation of hydrocarbons comprises an active phase and an auxiliary phase, wherein,
the general formula of the active phase is shown as a formula (I):
V 1 P x Mo y C z O u formula (I)
In the formula (I), the value range of x is 0.5-2, the value range of y is 0.01-0.1, the value range of z is 0-0.02, and u is the number of oxygen atoms meeting the valence of the active phase;
the auxiliary phase comprises molybdenum disulfide.
2. The catalyst according to claim 1, wherein the mass percentage of the active phase in the catalyst is 90-99.5% based on the total weight of the catalyst; the mass percentage of the auxiliary agent phase is 0.5% -5%.
3. The catalyst according to claim 1 or 2, characterized in that the mass percentage of carbon element in the catalyst is not more than 5%.
4. A catalyst according to any one of claims 1 to 3, wherein the compressive strength of the catalyst is from 15N to 30N.
5. A method of preparing the catalyst of any one of claims 1 to 4, comprising the steps of:
s1, reacting a reaction system containing a vanadium source, a phosphorus source and a solvent to obtain a post-reaction system;
s2, carrying out solid-liquid separation treatment on the reacted system to obtain precursor powder;
s3, mixing the precursor powder with molybdenum disulfide to obtain mixed powder;
s4, carrying out molding treatment on the mixed powder to obtain a catalyst precursor;
s5, activating the catalyst precursor to obtain the catalyst.
6. The method according to claim 5, wherein in step S1, the vanadium source is at least one selected from the group consisting of vanadium pentoxide, ammonium metavanadate and vanadium organic acid, preferably vanadium pentoxide; and/or
The phosphorus source is phosphoric acid, preferably 85-110 wt% phosphoric acid, more preferably 95-105 wt% phosphoric acid; and/or
The solvent is selected from at least one of monohydric alcohol and polyhydric alcohol, preferably a mixture of isobutanol and benzyl alcohol, preferably the molar ratio of isobutanol to benzyl alcohol in the mixture is 2:1-6:1; and/or
In the reaction system, the molar ratio of vanadium element to phosphorus element is (0.6-1.1): 1; and/or
In the reaction system, the ratio of the total mass of the solvent to the total mass of the vanadium source is (5-10): 1.
7. The method according to claim 5 or 6, wherein in step S1, the reaction conditions include: the temperature is 100-120 ℃.
8. The method according to any one of claims 5 to 7, wherein in step S3, the molybdenum disulfide is added in an amount of 0.5 to 5%, preferably 1 to 3% of the precursor powder.
9. The method according to any one of claims 5 to 8, wherein in step S4, the shaping treatment comprises subjecting the precursor powder to a first tabletting treatment, crushing, sieving and a second tabletting treatment in this order, preferably the sieving comprises sieving out catalyst particles having a particle size of 20 to 160 mesh and subjecting them to a subsequent second tabletting treatment.
10. The production method according to any one of claims 5 to 9, wherein in step S5, the activation treatment is performed under an atmosphere formed of one or more of an oxygen-containing gas, an inert gas, and water vapor; preferably, the inert gas is at least one of nitrogen, helium and argon; and/or
The temperature of the activation treatment is 370-480 ℃, and the time of the activation treatment is 1-20 h.
11. Use of a catalyst according to any one of claims 1 to 3 and/or a catalyst prepared by a method according to any one of claims 4 to 10 in the selective oxidation of hydrocarbons, in particular in the catalytic oxidation of n-butane to maleic anhydride.
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