CN107866246B - Hydrocarbon selective oxidation catalyst and preparation method thereof - Google Patents

Hydrocarbon selective oxidation catalyst and preparation method thereof Download PDF

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CN107866246B
CN107866246B CN201610846450.1A CN201610846450A CN107866246B CN 107866246 B CN107866246 B CN 107866246B CN 201610846450 A CN201610846450 A CN 201610846450A CN 107866246 B CN107866246 B CN 107866246B
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catalyst
precursor
acid
vanadium
roasting
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CN107866246A (en
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曾炜
顾龙勤
徐俊峰
赵欣
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride

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Abstract

The invention relates to a hydrocarbon selective oxidation catalyst and a preparation method thereof. The problem of the strong performance of the load VPO catalyst in the prior art is obviously reduced is solved. By adopting the following steps: 1) treating the selected catalyst support with a mineral acid; 2) adding a certain amount of vanadium-containing solution into the carrier prepared in the step 1, and soaking to obtain a precursor A; 3) mixing the precursor A, an organic solvent, phosphoric acid and a cocatalyst element compound, heating and keeping for 2-48h, filtering, washing and drying, and roasting at the temperature of not more than 300 ℃ for 1-20h to obtain a catalyst precursor B; 4) the supported catalyst is prepared by the technical scheme that the precursor B is roasted at the temperature of 350-500 ℃ in the atmosphere with special composition to obtain the final catalyst, has better load uniformity and higher activity selectivity, and can be used for the selective oxidation reaction of low-carbon hydrocarbons.

Description

Hydrocarbon selective oxidation catalyst and preparation method thereof
Technical Field
The invention relates to a hydrocarbon selective oxidation catalyst and a preparation method thereof, and the catalyst prepared by the method can be used for hydrocarbon selective oxidation reaction, and is particularly suitable for preparing maleic anhydride by selective oxidation of low-carbon alkane.
Technical Field
The gas phase selective oxidation of low carbon hydrocarbons is an important catalytic reaction. Can be used for preparing various oxidation products such as organic acid anhydride compounds and the like in a catalytic manner. One of the typical products is maleic anhydride (maleic anhydride).
The vanadium catalyst is one of the main catalyst systems for the gas phase selective oxidation reaction of low carbon hydrocarbons. It has been considered over the years that VPO catalysts are the most effective catalyst systems to date for the catalysis of gas phase hydrocarbons, especially n-butane, to maleic anhydride. Commercial VPO catalysts are usually prepared by aqueous or organic phase methods to produce the precursor vanadyl hydrogen phosphate hemihydrate (VOHPO)4·0.5H2And O), molding and roasting the obtained precursor to activate to obtain the final catalyst.
The aqueous phase VPO catalyst precursor is usually a pentavalent vanadium oxide such as vanadium pentoxide (V)2O5) Obtained by carrying out the reaction in the presence of water and HClThe former VPO catalyst precursor is mainly prepared by an organic phase method, the preparation process usually adopts pentavalent vanadium oxide and phosphoric acid to reflux in an organic solvent (mainly alcohols) to obtain the precursor, and the change state of vanadium in the process is that the pentavalent vanadium oxide is reduced into tetravalent vanadium oxide V by the organic alcohols2O4And the obtained tetravalent vanadium oxide and phosphoric acid are subjected to reflux reaction to obtain VOHPO4·0.5H2And O. The VPO catalyst prepared by the above preparation method has been commercialized, but the performance of the VPO catalyst still has some disadvantages. For example, VPO catalyst itself has weak strength and poor wear resistance, and the catalyst has small specific surface area, etc., and VPO supporting is one way to solve the above problems, for example, CN1935374 proposes ZrO2A method of loading VPO, Li et al propose a method of loading VPO on SBA-15 in "n-Butane oxidation over VPO catalysts supported on SBA-15" (Journal of Catalysis,2006,238, 232-241); Y.H.Taufiq-Yap et Al in "n-butyl Oxidation over gamma-Al2O3Supported Vanadium Phosphate Catalysts (Journal of Natural Gas Chemistry,2007,16,266-2O3A method of loading VPO, etc. However, most of the loading methods usually adopt a mode of adding a carrier into a VPO precursor solution to realize impregnation loading, and since the VPO precursor solution prepared by an organic method is usually in a suspension state, the uniformity of the loading is usually limited to a certain extent, and the performance of the loaded catalyst is influenced. Therefore, it is a development direction of the supported VPO catalyst to solve the problem of uniform and good loading of the VPO catalyst and to ensure that the activity selectivity of the catalyst can be maintained after loading.
Disclosure of Invention
The invention aims to solve the problem that the strong performance of a supported VPO catalyst is obviously reduced in the prior art, and provides a preparation method of a supported vanadium-phosphorus catalyst for selective oxidation reaction of hydrocarbons. The supported vanadium-phosphorus catalyst prepared by the method is more uniform in loading and better in catalytic performance.
In order to solve the technical problems, the catalyst comprises the following components in percentage by weight:
A) 35-55% of a carrier compound;
B) 40-60% of active catalytic component; the active component has the following composition general formula in terms of element molar ratio: VPaXbYcZdOe, wherein X is at least one element selected from transition metal elements; y is at least one element selected from alkali metals or alkaline earth metals; z is at least one element selected from group IVA or VA;
wherein a is 0.9-1.4; b is 0.001-0.3; c is 0-0.2; d is 0-0.1; e is the molar ratio of oxygen elements required to satisfy the valences of the elements in the composition.
In the above technical solution, X is selected from at least one element of transition metals, and preferably one or more of Mo, Zn, Nb, Co, Zr elements are used.
In the above embodiment, Y is at least one element selected from alkali metals and alkaline earth metals, and preferably Li or Na is used.
In the above embodiment, Z is selected from at least one element of group IVA or VA, and Si or Bi is preferably used.
In the above technical solution, X is preferably selected from Mo and Zn; y is selected from Na; z is selected from Bi.
The preparation method of the catalyst adopts the technical scheme that the preparation method comprises the following steps:
1) mixing the selected catalyst carrier with inorganic acid, heating, stirring, reacting for 2-24h, filtering and drying;
2) heating and dissolving a certain amount of vanadium compound in an oxalic acid solution, adding the carrier prepared in the step 1 for impregnation after the dissolution reaction is finished, drying the impregnated carrier, and roasting at the temperature of 500-600 ℃ for 1-24h to obtain a precursor A;
3) mixing the precursor A, an organic solvent, phosphoric acid and a cocatalyst, adding the mixture into an autoclave, sealing and heating for 2-48h, filtering, washing and drying the obtained product, and roasting at the temperature of not more than 300 ℃ for 1-20h to obtain a catalyst precursor B;
4) and roasting the precursor B in the atmosphere with special composition at the temperature of 350-500 ℃ to obtain the final catalyst.
In the above technical solution, the catalyst carrier in step 1) is a porous oxide that is not easily soluble in the acid used, and may include inorganic oxides, composite oxides, molecular sieves, and other carriers, and typical characteristics of the selected carrier should include good physical strength and large specific surface area. The specific surface area of the oxide carrier should be more than 50m2(ii) in terms of/g. Preferably, the oxide support is a composite oxide support. In the above-described aspect, the composite carrier preferably contains a mixed element of Ti and Zr.
In the above technical solution, the inorganic acid in step 1) may be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or the like. In the present production method, phosphoric acid is preferably used.
In the above technical solution, the vanadium compound in step 2) mainly refers to a tetravalent or pentavalent compound of vanadium, and the selected vanadium compound and the corresponding solvent preferably can form a homogeneous solution, so as to achieve uniform loading of the vanadium compound.
In the above technical scheme, the organic solvent in step 3) mainly comprises one or more of primary alcohols, secondary alcohols, polyols, organic amines and organic acid compounds, and the preferred technical scheme is to adopt a primary alcohol solvent; more preferably, the organic solvent is a single or mixed system of isobutanol and benzyl alcohol.
In the above technical scheme, the cocatalyst in step 3) is a compound of X, Y, Z element in the composition of the catalyst active component. The compound of the element may be an inorganic salt or an organic salt of the element, and is preferably a corresponding salt compound soluble in the organic solvent used. Before contacting with the precursor A in the above technical scheme, the optional elements should be fully mixed with the organic solvent and the phosphorus-containing compound in the step 3).
In the above technical scheme, the molar ratio of the phosphorus element contained in the phosphoric acid in the step 3) to the vanadium element content in the precursor A should be controlled to be 0.9-1.3.
The technical scheme is characterized in that an autoclave is adopted in the step 3) for carrying out reduction reaction of the supported catalyst. The reduction reaction is realized through temperature control to generate a precursor, and the desorption of the impregnation layer is reduced through the high-pressure kettle environment, so that the performance of the catalyst is improved. The temperature range of the autoclave is controlled to be 100-200 ℃, and preferably 120-160 ℃.
In the technical scheme, the process of obtaining the active catalyst through heat treatment in the step 4) under a special atmosphere is that the special atmosphere is mixed gas of light hydrocarbon/air, or mixed gas of air/inert gas/water vapor, or mixed gas of air/inert gas/carbon oxide/water vapor, and the activation temperature is 350-500 ℃. The more preferable technical scheme is that the activation temperature of the heat treatment activation process is 380-450 ℃. The light hydrocarbon mainly refers to low-carbon alkane, preferably n-butane; the inert gas can be nitrogen, helium or argon; the carbon oxide is mainly carbon dioxide.
By adopting the technical scheme of the invention, the supported VPO catalyst prepared by using the preparation method that the catalyst carrier treated by acid is firstly uniformly loaded with vanadium oxide, then heated in a high-pressure kettle for reaction and reduction, added with a plurality of catalyst promoters and finally roasted and activated in a special atmosphere has better load uniformity and higher activity selectivity, can be used for selective oxidation reaction of low-carbon hydrocarbons, and is particularly suitable for preparing maleic anhydride by selective oxidation of n-butane.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Detailed Description
[ example 1 ]
0.025mol of titanium tetrachloride and 0.075mol of zirconium oxychloride are dissolved in deionized water under ice bath conditions to prepare a solution with the concentration of 0.5M. Dropping the obtained solution into 25 wt% ammonia water solution under stirring, detecting the pH value of the solution, stopping dropping and stirring when the pH value reaches about 9, standing at room temperature for aging overnight, filtering, washing with deionized water until no Cl ions are detected in silver nitrate solution, and drying at 120 ℃ for 20 h. Adding the dried composite oxide into a phosphoric acid solution with the concentration of about 1M, heating to 80 ℃, stirring and keeping for 10 hours, filtering and washing the obtained acid-treated composite oxide, drying in an oven at 120 ℃, and roasting in a muffle furnace at 500 ℃ for 6 hours to obtain the composite oxide carrier.
Adding 0.6mol of oxalic acid into 500ml of deionized water for dissolving, adding 0.2mol of ammonium metavanadate into the oxalic acid, heating the solution and stirring for dissolving, adding 20g of carrier into the dissolved vanadium solution, soaking for 20h, filtering, drying at 120 ℃ for 20h, and roasting in a muffle furnace at 550 ℃ for 6h to obtain a catalyst precursor A.
Adding 0.3mol of precursor A based on the molar amount of vanadium, 400ml of isobutanol, 100ml of benzyl alcohol, 95 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is about 1.05), 0.003mol of phosphomolybdic acid, 0.01mol of zinc acetylacetonate, 0.0005mol of sodium oxalate and 0.001mol of bismuth acetate into an autoclave, heating the autoclave to 140 ℃, reacting for 10 hours, cooling, filtering, washing with isobutanol, drying the obtained filter cake at 110 ℃ for 20 hours, and roasting at 260 ℃ in an air atmosphere for 6 hours to obtain precursor B. And (3) heating the precursor B to 425 ℃ in an atmosphere of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor by volume, roasting for 3h, and finally roasting for 3h at 425 ℃ in an atmosphere of 40% nitrogen/10% carbon dioxide/50% water vapor to obtain the active catalyst. The resulting catalyst was charged at 1.5 vol% butane for 1600hr-1Space velocity, evaluated in a fixed bed reactor at 390 c, measured a butane conversion of 84.7% and a maleic anhydride yield of 58.2%.
Comparative example 1
Adding 0.3mol of vanadium pentoxide, 400ml of isobutanol, 100ml of benzyl alcohol, 95 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is about 1.05), 0.003mol of phosphomolybdic acid, 0.01mol of zinc acetylacetonate, 0.0005mol of sodium oxalate and 0.001mol of bismuth acetate into an autoclave, heating the autoclave to 140 ℃, reacting for 10 hours, cooling, filtering, washing with isobutanol, drying the obtained filter cake at 110 ℃ for 20 hours, and roasting at 260 ℃ in an air atmosphere for 6 hours to obtain a precursor B. The precursor B is heated to 425 ℃ in an atmosphere with the volume ratio of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor for roasting for 3h, and finally, the precursor B is roasted in an atmosphere with the volume ratio of 40% nitrogen/10% carbon dioxideAnd/50% water vapor roasting at 425 deg.c for 3 hr to obtain the active catalyst. The resulting catalyst was charged at 1.5 vol% butane for 1600hr-1Space velocity, evaluated in a fixed bed reactor at 390 c, measured a butane conversion of 82.9% and a maleic anhydride yield of 54.3%.
[ example 2 ]
0.025mol of titanium tetrachloride and 0.075mol of zirconium oxychloride are dissolved in deionized water under ice bath conditions to prepare a solution with the concentration of 0.5M. Dropping the obtained solution into 25 wt% ammonia water solution under stirring, detecting the pH value of the solution, stopping dropping and stirring when the pH value reaches about 9, standing at room temperature for aging overnight, filtering, washing with deionized water until no Cl ions are detected in silver nitrate solution, and drying at 120 ℃ for 20 h. Adding the dried composite oxide into a phosphoric acid solution with the concentration of about 1M, heating to 80 ℃, stirring and keeping for 10 hours, filtering and washing the obtained acid-treated composite oxide, drying in an oven at 120 ℃, and roasting in a muffle furnace at 500 ℃ for 6 hours to obtain the composite oxide carrier.
Adding 0.6mol of oxalic acid into 500ml of deionized water for dissolving, adding 0.2mol of ammonium metavanadate into the oxalic acid, heating the solution and stirring for dissolving, adding 20g of carrier into the dissolved vanadium solution, soaking for 20h, filtering, drying at 120 ℃ for 20h, and roasting in a muffle furnace at 550 ℃ for 6h to obtain a catalyst precursor A.
Adding 0.3mol of the precursor A, based on the molar amount of vanadium, into a high-pressure autoclave together with 400ml of isobutanol, 100ml of benzyl alcohol, 95 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is about 1.05), 0.003mol of phosphomolybdic acid and 0.01mol of zinc acetylacetonate which are mixed, heating the high-pressure autoclave to 140 ℃ for reaction for 10 hours, cooling, filtering, washing with isobutanol, drying the obtained filter cake at 110 ℃ for 20 hours, and roasting at 260 ℃ for 6 hours in an air atmosphere to obtain a precursor B. And (3) heating the precursor B to 425 ℃ in an atmosphere of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor by volume, roasting for 3h, and finally roasting for 3h at 425 ℃ in an atmosphere of 40% nitrogen/10% carbon dioxide/50% water vapor to obtain the active catalyst. The resulting catalyst was charged at 1.5 vol% butane for 1600hr-1The space velocity is evaluated in a fixed bed reactor at 390 ℃, and the butane conversion rate is measured to be 83.1 percent, and the maleic anhydride is recoveredThe rate was 57.0%.
[ example 3 ]
20g of ZrO2Adding into 1M phosphoric acid solution, heating to 80 deg.C, stirring for 8 hr to obtain acid-treated ZrO2After being filtered and washed, the mixture is dried in an oven at 120 ℃ and is placed in a muffle furnace to be roasted for 6 hours at 500 ℃ to obtain the oxide carrier.
Adding 0.6mol of oxalic acid into 500ml of deionized water for dissolving, adding 0.2mol of ammonium metavanadate into the oxalic acid, heating the solution and stirring for dissolving, adding 20g of carrier into the dissolved vanadium solution, soaking for 20h, filtering, drying at 120 ℃ for 20h, and roasting in a muffle furnace at 550 ℃ for 6h to obtain a catalyst precursor A.
Adding 0.3mol of precursor A based on the molar amount of vanadium, 400ml of isobutanol, 100ml of benzyl alcohol, 95 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is about 1.05), 0.003mol of phosphomolybdic acid, 0.01mol of zinc acetylacetonate, 0.0005mol of sodium oxalate and 0.001mol of bismuth acetate into an autoclave, heating the autoclave to 140 ℃, reacting for 10 hours, cooling, filtering, washing with isobutanol, drying the obtained filter cake at 110 ℃ for 20 hours, and roasting at 260 ℃ in an air atmosphere for 6 hours to obtain precursor B. And (3) heating the precursor B to 425 ℃ in an atmosphere of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor by volume, roasting for 3h, and finally roasting for 3h at 425 ℃ in an atmosphere of 40% nitrogen/10% carbon dioxide/50% water vapor to obtain the active catalyst. The resulting catalyst was charged at 1.5 vol% butane for 1600hr-1Space velocity, evaluated in a fixed bed reactor at 390 ℃, determined to be 82.5% butane conversion and 55.3% maleic anhydride yield.
[ example 4 ]
0.025mol of titanium tetrachloride and 0.075mol of zirconium oxychloride are dissolved in deionized water under ice bath conditions to prepare a solution with the concentration of 0.5M. Dropping the obtained solution into 25 wt% ammonia water solution under stirring, detecting the pH value of the solution, stopping dropping and stirring when the pH value reaches about 9, standing at room temperature for aging overnight, filtering, washing with deionized water until no Cl ions are detected in silver nitrate solution, and drying at 120 ℃ for 20 h. Adding the dried composite oxide into a phosphoric acid solution with the concentration of about 1M, heating to 80 ℃, stirring and keeping for 10 hours, filtering and washing the obtained acid-treated composite oxide, drying in an oven at 120 ℃, and roasting in a muffle furnace at 500 ℃ for 6 hours to obtain the composite oxide carrier.
Adding 0.6mol of oxalic acid into 500ml of deionized water for dissolving, adding 0.2mol of ammonium metavanadate into the oxalic acid, heating the solution and stirring for dissolving, adding 20g of carrier into the dissolved vanadium solution, soaking for 20h, filtering, drying at 120 ℃ for 20h, and roasting in a muffle furnace at 550 ℃ for 6h to obtain a catalyst precursor A.
Adding 0.3mol of precursor A based on the molar amount of vanadium, 400ml of isobutanol, 100ml of benzyl alcohol, 95 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is about 0.9), 0.003mol of phosphomolybdic acid, 0.01mol of zinc acetylacetonate, 0.0005mol of sodium oxalate and 0.001mol of bismuth acetate into an autoclave, heating the autoclave to 140 ℃, reacting for 10 hours, cooling, filtering, washing with isobutanol, drying the obtained filter cake at 110 ℃ for 20 hours, and roasting at 260 ℃ in an air atmosphere for 6 hours to obtain precursor B. And (3) heating the precursor B to 425 ℃ in an atmosphere of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor by volume, roasting for 3h, and finally roasting for 3h at 425 ℃ in an atmosphere of 40% nitrogen/10% carbon dioxide/50% water vapor to obtain the active catalyst. The resulting catalyst was charged at 1.5 vol% butane for 1600hr-1Space velocity, evaluated in a fixed bed reactor at 390 c, measured a butane conversion of 89.6% and a maleic anhydride yield of 54.7%.
[ example 5 ]
0.025mol of titanium tetrachloride and 0.075mol of zirconium oxychloride are dissolved in deionized water under ice bath conditions to prepare a solution with the concentration of 0.5M. Dropping the obtained solution into 25 wt% ammonia water solution under stirring, detecting the pH value of the solution, stopping dropping and stirring when the pH value reaches about 9, standing at room temperature for aging overnight, filtering, washing with deionized water until no Cl ions are detected in silver nitrate solution, and drying at 120 ℃ for 20 h. Adding the dried composite oxide into a phosphoric acid solution with the concentration of about 1M, heating to 80 ℃, stirring and keeping for 10 hours, filtering and washing the obtained acid-treated composite oxide, drying in an oven at 120 ℃, and roasting in a muffle furnace at 500 ℃ for 6 hours to obtain the composite oxide carrier.
Adding 0.6mol of oxalic acid into 500ml of deionized water for dissolving, adding 0.2mol of ammonium metavanadate into the oxalic acid, heating the solution and stirring for dissolving, adding 20g of carrier into the dissolved vanadium solution, soaking for 20h, filtering, drying at 120 ℃ for 20h, and roasting in a muffle furnace at 550 ℃ for 6h to obtain a catalyst precursor A.
Adding 0.3mol of precursor A based on the molar amount of vanadium, 400ml of isobutanol, 100ml of benzyl alcohol, 95 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is about 1.05), 0.003mol of phosphomolybdic acid, 0.01mol of zinc acetylacetonate, 0.0005mol of sodium oxalate and 0.001mol of bismuth acetate into an autoclave, heating the autoclave to 120 ℃, reacting for 10 hours, cooling, filtering, washing with isobutanol, drying the obtained filter cake at 110 ℃ for 20 hours, and roasting at 260 ℃ in an air atmosphere for 6 hours to obtain precursor B. And (3) heating the precursor B to 425 ℃ in an atmosphere of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor by volume, roasting for 3h, and finally roasting for 3h at 425 ℃ in an atmosphere of 40% nitrogen/10% carbon dioxide/50% water vapor to obtain the active catalyst. The resulting catalyst was charged at 1.5 vol% butane for 1600hr-1Space velocity, evaluated in a fixed bed reactor at 390 c, measured a butane conversion of 83.5% and a maleic anhydride yield of 56.1%.
[ example 6 ]
0.025mol of titanium tetrachloride and 0.075mol of zirconium oxychloride are dissolved in deionized water under ice bath conditions to prepare a solution with the concentration of 0.5M. Dropping the obtained solution into 25 wt% ammonia water solution under stirring, detecting the pH value of the solution, stopping dropping and stirring when the pH value reaches about 9, standing at room temperature for aging overnight, filtering, washing with deionized water until no Cl ions are detected in silver nitrate solution, and drying at 120 ℃ for 20 h. Adding the dried composite oxide into a phosphoric acid solution with the concentration of about 1M, heating to 80 ℃, stirring and keeping for 10 hours, filtering and washing the obtained acid-treated composite oxide, drying in an oven at 120 ℃, and roasting in a muffle furnace at 500 ℃ for 6 hours to obtain the composite oxide carrier.
Adding 0.6mol of oxalic acid into 500ml of deionized water for dissolving, adding 0.2mol of ammonium metavanadate into the oxalic acid, heating the solution and stirring for dissolving, adding 20g of carrier into the dissolved vanadium solution, soaking for 20h, filtering, drying at 120 ℃ for 20h, and roasting in a muffle furnace at 550 ℃ for 6h to obtain a catalyst precursor A.
Adding 0.3mol of precursor A based on the molar amount of vanadium, 500ml of isobutanol, 95 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is about 1.05), 0.003mol of phosphomolybdic acid, 0.01mol of zinc acetylacetonate, 0.0005mol of sodium oxalate and 0.001mol of bismuth acetate into an autoclave, heating the autoclave to 140 ℃, reacting for 10 hours, cooling, filtering, washing with isobutanol, drying the obtained filter cake at 110 ℃ for 20 hours, and roasting at 260 ℃ for 6 hours in an air atmosphere to obtain precursor B. And (3) heating the precursor B to 425 ℃ in an atmosphere of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor by volume, roasting for 3h, and finally roasting for 3h at 425 ℃ in an atmosphere of 40% nitrogen/10% carbon dioxide/50% water vapor to obtain the active catalyst. The resulting catalyst was charged at 1.5 vol% butane for 1600hr-1Space velocity, evaluated in a fixed bed reactor at 390 c, measured a butane conversion of 84.1% and a maleic anhydride yield of 57.2%.

Claims (7)

1. A hydrocarbon selective oxidation catalyst comprising, in weight percent based on the total weight of the catalyst:
A) 35-55% of a carrier compound;
B) 40-60% of active catalytic component; the active component has the following composition general formula in terms of element molar ratio:
VPaXbYcZdOe
wherein X is at least one element selected from transition metal elements;
y is at least one element selected from alkali metals or alkaline earth metals;
z is at least one element selected from group IVA or VA;
wherein a is 0.9-1.4;
b＝0.001～0.3；
c＝0～0.2；
d＝0～0.1；
e is the molar ratio of oxygen elements required to satisfy the valence of each element in the composition; the preparation method of the catalyst comprises the following steps:
1) mixing the selected catalyst carrier with inorganic acid, heating, stirring, reacting for 2-24h, filtering and drying;
2) heating and dissolving a metered vanadium compound in an oxalic acid solution, adding the carrier prepared in the step 1 for impregnation after the dissolution reaction is finished, drying the impregnated carrier, and roasting at the temperature of 500-600 ℃ for 1-24h to obtain a precursor A;
3) mixing the precursor A, an organic solvent, phosphoric acid and a cocatalyst, adding into an autoclave, hermetically heating at 100-200 ℃ for 2-48h, filtering, washing and drying the obtained product, and roasting at the temperature of not more than 300 ℃ for 1-20h to obtain a catalyst precursor B;
4) roasting the precursor B in an atmosphere with a specific composition at the temperature of 350-500 ℃ to obtain a final catalyst; the specific composition atmosphere refers to a mixed atmosphere of light hydrocarbon/air, or a mixed atmosphere of air/inert gas/water vapor, or a mixed atmosphere of air/inert gas/carbon oxide/water vapor.
2. The selective hydrocarbon oxidation catalyst according to claim 1, wherein the catalyst carrier in step 1 is a porous oxide which is not easily soluble in the acid used, and is at least one selected from the group consisting of inorganic oxides, composite oxides and molecular sieves, and the carrier has a specific surface area of more than 50m2/g。
3. The hydrocarbon selective oxidation catalyst of claim 1, wherein the inorganic acid in step 1 is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
4. The hydrocarbon selective oxidation catalyst as set forth in claim 1, wherein the vanadium compound in step 2 is selected from the group consisting of tetravalent and pentavalent compounds of vanadium.
5. The selective hydrocarbon oxidation catalyst according to claim 1, wherein the organic solvent in step 3 is one or more selected from the group consisting of primary alcohols, secondary alcohols, polyols, organic amines, and organic acids.
6. The selective hydrocarbon oxidation catalyst according to claim 1, wherein the phosphoric acid and the precursor a in step 3 have a phosphorus to vanadium element ratio of 0.9 to 1.3.
7. The hydrocarbon selective oxidation catalyst as claimed in claim 1, wherein the light hydrocarbon is a C1-C5 light alkane; the inert gas is selected from nitrogen, helium or argon.
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