CN114100651A - Catalyst for preparing maleic anhydride through benzene oxidation and preparation method and application thereof - Google Patents

Catalyst for preparing maleic anhydride through benzene oxidation and preparation method and application thereof Download PDF

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CN114100651A
CN114100651A CN202010863579.XA CN202010863579A CN114100651A CN 114100651 A CN114100651 A CN 114100651A CN 202010863579 A CN202010863579 A CN 202010863579A CN 114100651 A CN114100651 A CN 114100651A
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catalyst
compound
maleic anhydride
benzene
molar amount
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CN114100651B (en
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张东顺
师慧敏
张作峰
冯晔
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • B01J27/228—Silicon carbide with phosphorus, arsenic, antimony or bismuth
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst for preparing maleic anhydride by benzene oxidation, a preparation method and application thereof. The invention adopts the non-metal auxiliary agent boron, and can adjust the acid strength of the surface of the catalyst, thereby being beneficial to the adsorption of benzene and the desorption of maleic anhydride, and being more beneficial to the improvement of the selectivity of the maleic anhydride, thereby improving the performance of the catalyst. Meanwhile, the performance of the catalyst can be further improved by compounding the non-metal boron and the metal auxiliary agent, combining a binder to fix the active component and using ammonium carbonate or ammonium bicarbonate.

Description

Catalyst for preparing maleic anhydride through benzene oxidation and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst for preparing maleic anhydride by benzene oxidation.
Background
Maleic anhydride (maleic anhydride) is a very important organic chemical raw material, and is the second largest organic anhydride which is second only to phthalic anhydride. The method has wide main application, can be used for producing 1, 4-butanediol, tetrahydrofuran, gamma-butyrolactone, malic acid, unsaturated polyester resin and the like, and can also be used as a raw material of medicines and pesticides. Unsaturated Polyester Resin (UPR) is the largest downstream consumer product of maleic anhydride, and is followed by 1, 4-butanediol, and the consumption of the two can account for more than 60% of the total consumption of the maleic anhydride.
The production process of maleic anhydride can be divided into benzene and n-butane methods according to the variety of raw materials. In recent years, the productivity of the domestic n-butane oxidation method device is continuously expanded, the development momentum is fast, but the process for preparing maleic anhydride by the n-butane method is more complex than that of the benzene method, and the operation is relatively difficult, so that the process using the benzene as the raw material still can account for 50 percent of the total production energy of the maleic anhydride. In addition, the price of benzene is gradually reduced along with the price reduction of maleic anhydride in 2019, the price of n-butane is not changed greatly, the market price of n-butane is currently 4000 yuan/ton, the price of benzene is 4500 yuan/ton, the price difference between the two is very small, and when the price difference between the price of raw material benzene and the ton price of n-butane is within 1500 yuan in combination with the operation cost of a benzene method and a butane method maleic anhydride device, the comprehensive cost advantage of the benzene method is higher than that of the n-butane method.
In areas with relatively rich coal resources and relatively deficient petroleum resources, such as the inner landlands of Shanxi province and the like, the maleic anhydride device adopting the coking benzene as the raw material still has very large capacity due to the large amount of coking benzene as the byproduct. At present, because the original cost and the price difference of the maleic anhydride product are small, the production of enterprises have great competition, manufacturers reduce the production cost as much as possible in order to improve the economic benefit, the raw material cost of the benzene occupies more than 80 percent of the production cost of the maleic anhydride, the benzene consumption is reduced, the by-product of the benzene is reduced, the selectivity of the maleic anhydride is improved, the utilization rate of the benzene is improved, and the economic benefit can be obviously improved.
At present, patents for preparing maleic anhydride catalysts by benzene oxidation mainly focus on screening of metal additives and optimization of a formula, for example, patent CN103816931A proposes a preparation method of maleic anhydride catalysts by benzene oxidation, in which molybdenum compounds and vanadium compounds are dissolved in hydrochloric acid, then a solution containing compounds such as phosphorus, sodium, nickel, copper and the like is added into the active hydrochloric acid, and the obtained solution is sprayed on an inert talc ceramic carrier, and then activated at the temperature of 350-450 ℃ in an inert gas atmosphere to obtain the active catalyst. However, hydrochloric acid is a very volatile and corrosive acid, which not only causes equipment corrosion and increases equipment cost, but also damages worker health and causes a series of problems of environmental pollution and the like.
Patent CN105536837A also discloses a catalyst for preparing maleic anhydride by benzene oxidation, which is prepared by using rare earth metal oxide as a main additive, such as one or more of lanthanum, cerium, terbium, europium and the like, and silicon carbide as a carrier by using an impregnation method or a spraying method.
At present, published patents are focused on the research of metal additives, especially rare earth metal additives, while relatively few researches on non-metal additives are carried out, and patent CN101284242A indicates that P is increased appropriately in the catalyst2O5Based on the thought, the catalyst prepared by the method adopts a non-metal auxiliary agent, and meanwhile, a rare earth metal auxiliary agent is not added, so that the acid strength of the catalyst is further reduced, and the selectivity of the maleic anhydride is further improved under the condition that the activity is kept at a high level.
Disclosure of Invention
The reaction for preparing maleic anhydride by benzene oxidation belongs to gas-solid reaction, wherein benzene adsorption and maleic anhydride adsorption play very important roles in the reaction process, the benzene adsorption and maleic anhydride desorption time is too long, deep oxidation is easy, and products mainly comprise carbon dioxide and carbon monoxide. Research shows that during the adsorption and desorption of benzene and maleic anhydride, the acid center plays a very important role, but the acid center cannot be too strong, and if the acid center is too strong, the adsorption and desorption time of benzene and maleic anhydride is too long, and the benzene and maleic anhydride are easily deeply oxidized under the action of lattice oxygen, so that the selectivity of maleic anhydride is reduced. Therefore, the adjustment and control of the strength of the acid center are very critical to the improvement of the performance of the catalyst.
In order to overcome the problems in the prior art, the invention provides a catalyst for preparing maleic anhydride by benzene oxidation, and a boron-containing compound is introduced during the preparation of the catalyst3The hybridization orbit, thus form the skeleton boric acid center of tetrahedral coordination, its acidity is weaker, it is the weak acid center, help benzene absorption and desorption of cis-anhydride, therefore the invention uses boron as one of the adjuvants, to improve the selectivity of cis-anhydride.
One of the purposes of the invention is to provide a catalyst for preparing maleic anhydride by benzene oxidation, which comprises a carrier and an active component loaded on the carrier, wherein the active component comprises a main catalyst and an auxiliary catalyst, and the auxiliary catalyst comprises boron and at least one of indium, antimony and bismuth.
According to research, at least one of indium, antimony and bismuth is used as a metal additive, and the metal additive has an obvious promotion effect on the improvement of the selectivity of the catalyst, so that the invention adopts the compatibility of a non-metal element boron and metal elements indium, antimony and bismuth, and improves the selectivity of the catalyst together through the synergistic effect of boron and the metals so as to obtain better weight yield of maleic anhydride, and the weight yield of the maleic anhydride can reach 100% under evaluation conditions.
The invention aims to solve the problem of low maleic anhydride selectivity in the prior art, boron is adopted to adjust the acid strength of the catalyst, a metal auxiliary agent is adopted to further improve the maleic anhydride selectivity, and the performances of the catalyst are jointly improved under the compatibility of the non-metal auxiliary agent and the metal auxiliary agent.
In a preferred embodiment, the support is selected from at least one of silicon carbide, alumina and silica.
In a further preferred embodiment, the shape of the carrier is any one of a spherical shape, a cylindrical shape, an annular shape, a clover shape, and a clover shape.
In a preferred embodiment, the loading of the active component is 10-20%, preferably 14-18% based on the catalyst.
Wherein, the activity of the catalyst is affected due to insufficient loading of the active component, the benzene conversion rate is too low, the active component is loaded too much, the deep oxidation of the catalyst is serious, the number of byproducts is large, and the weight yield of the maleic anhydride is reduced.
In a preferred embodiment, the main catalyst includes vanadium, molybdenum, sodium, phosphorus and nickel.
In a preferred embodiment, the vanadium element is derived from at least one of ammonium metavanadate, vanadyl oxalate, vanadium pentoxide and sodium vanadate.
In a preferred embodiment, the molybdenum element is derived from at least one of ammonium molybdate, molybdenum trioxide and calcium molybdate, and is preferably ammonium molybdate.
In a preferred embodiment, the sodium element is derived from at least one of sodium dihydrogen phosphate and trisodium phosphate, preferably trisodium phosphate.
In a preferred embodiment, the phosphorus element is at least one of ammonium dihydrogen phosphate, 85% -115% phosphoric acid and phosphorus pentoxide, and is preferably ammonium dihydrogen phosphate.
In a preferred embodiment, the nickel element is at least one selected from nickel nitrate, nickel sulfate, nickel chloride and nickel oxide, and is preferably nickel nitrate.
In a preferred embodiment, the boron element is derived from at least one of boric acid, boric oxide, and sodium borate.
In a preferred embodiment, the indium element, the antimony element and the bismuth element are derived from at least one of soluble salts containing the elements.
In a further preferred embodiment, the indium element, the antimony element, and the bismuth element are derived from at least one of an acetate, a nitrate, and a chloride containing the elements.
In a most preferred embodiment, the promoter comprises at least two (e.g., two) of an indium element, an antimony element, and a bismuth element and a boron element (e.g., selected from an indium element, an antimony element, and a boron element, or selected from an antimony element, a bismuth element, and a boron element, or selected from an indium element, a bismuth element, and a boron element). Wherein the molar ratio of the two metal elements is between (0.01-100):1, preferably (0.1-20):1, more preferably (0.1-10):1, for example (0.1-5): 1.
The inventors have found through a large number of experiments that when at least two elements selected from the indium element, the antimony element, and the bismuth element are selected, the effect is apparently due to the selection of one of them.
In a preferred embodiment, the molar ratio of the vanadium element, the molybdenum element, the sodium element, the phosphorus element, the nickel element, the boron element and the M element is 1 (0.2-0.90): 0.001-0.2): 0.005-0.25): 0.0001-0.05): 0.001-0.06): 0.0001-0.05), wherein V is the molar ratio of the molybdenum element to the M element, and V is the molar ratio of the molybdenum element to the M element, and M is the molar ratio of the molybdenum element to the M element, and V is the molar ratio of the molybdenum element to the sodium element to the phosphorus element, and the nickel element to the M element, wherein V is the molar ratio of the molybdenum element to the M element to the molybdenum element to the M element, and the molybdenum element to the molybdenum element, and the M element to the molybdenum element, and the molybdenum element to the M element, and the molybdenum element to the M element to the molybdenum2O5Calculated in mol as MoO3In terms of molar amount, as Na2Molar amount of O in P2O5Calculated as molar amount, calculated as molar amount of NiO, calculated as B2O3Molar amount, based on the molar amount of the M element, when M is selected from the two promoter metals, M is based on the sum of the molar amounts of the two promoter metals.
In a further preferred embodiment, the molar ratio of the vanadium element, the molybdenum element, the sodium element, the phosphorus element, the nickel element, the boron element and the M element is 1 (0.3-0.80): 0.01-0.1: (0.005-0.03): 0.002-0.02): 0.005-0.02), wherein V is respectively2O5Calculated in mol as MoO3In terms of molar amount, as Na2Molar amount of O in P2O5Calculated as molar amount, calculated as molar amount of NiO, calculated as B2O3Molar amount, based on the molar amount of the M element, when M is selected from the two promoter metals, M is based on the sum of the molar amounts of the two promoter metals.
The second purpose of the invention is to provide a preparation method of the catalyst for preparing maleic anhydride by benzene oxidation, which comprises the following steps:
step 1, adding a compound containing an active component into a reducing agent solution to obtain an active mother liquor;
step 2, contacting the active mother liquor with a carrier, and drying to obtain a catalyst precursor;
and 3, activating the catalyst precursor to obtain the maleic anhydride catalyst prepared by benzene oxidation.
In a preferred embodiment, the active component-containing compound includes a procatalyst compound and a cocatalyst compound.
In a further preferred embodiment, the procatalyst compound includes a vanadium compound, a molybdenum compound, a sodium compound, a phosphorous compound and a nickel compound.
In a still further preferred embodiment, the promoter compound comprises a boron-containing compound and a M-containing compound, M being selected from at least one of indium, antimony and bismuth.
In a preferred embodiment, the vanadium compound is selected from at least one of ammonium metavanadate, vanadyl oxalate, vanadium pentoxide and sodium vanadate.
In a preferred embodiment, the molybdenum compound is selected from at least one of ammonium molybdate, molybdenum trioxide, calcium molybdate, preferably ammonium molybdate.
In a preferred embodiment, the sodium compound is selected from at least one of monosodium phosphate, trisodium phosphate, preferably trisodium phosphate.
In a preferred embodiment, the phosphorus compound is selected from at least one of monoammonium phosphate, 85% -115% phosphoric acid, phosphorus pentoxide, preferably monoammonium phosphate.
In a preferred embodiment, the nickel compound is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, and nickel oxide, preferably nickel nitrate.
In a preferred embodiment, the boron-containing compound is selected from at least one of boric acid, boric oxide and sodium borate.
In a preferred embodiment, the M-containing compound is selected from at least one of soluble salts of M-containing elements.
In a further preferred embodiment, the M element is derived from at least one of acetate, nitrate and chloride salts of the M-containing element.
In a preferred embodiment, the molar ratio of the vanadium compound, molybdenum compound, sodium compound, phosphorus compound, nickel compound, boron-containing compound and M-containing compound is 1 (0.2-0.90): 0.001-0.2): 0.005-0.25): 0.0001-0.05): 0.001-0.06): 0.0001-0.05) wherein V is added2O5Calculated in mol as MoO3In terms of molar amount, as Na2Molar amount of O in P2O5Calculated as molar amount, calculated as molar amount of NiO, calculated as B2O3Molar amount, based on the molar amount of the M element, when M is selected from the two promoter metals, M is based on the sum of the molar amounts of the two promoter metals.
In a further preferred embodiment, the molar ratio of the vanadium compound, molybdenum compound, sodium compound, phosphorus compound, nickel compound, boron-containing compound and M-containing compound is 1 (0.3-0.80): 0.01-0.1): 0.005-0.03): 0.002-0.02): 0.005-0.02), wherein V is the molar ratio of V to the molar ratio of the boron-containing compound to the M-containing compound2O5Calculated in mol as MoO3In terms of molar amount, as Na2Molar amount of O in P2O5Calculated as molar amount, calculated as molar amount of NiO, calculated as B2O3Molar amount, based on the molar amount of the M element, when M is selected from the two promoter metals, M is based on the sum of the molar amounts of the two promoter metals.
The invention aims to solve the problem of low maleic anhydride selectivity in the prior art, boron is adopted to adjust the acid strength of the catalyst, a metal auxiliary agent M is adopted to further improve the maleic anhydride selectivity, and the performances of the catalyst are jointly improved under the compatibility of the non-metal auxiliary agent and the metal auxiliary agent M.
In a preferred embodiment, in step 1, the reducing agent is selected from oxalic acid.
In a further preferred embodiment, in the step 1, the molar ratio of the reducing agent to the vanadium compound is (1-3): 1, preferably (1.5-2.5): 1.
In a preferred embodiment, in step 2, the carrier is subjected to a heat treatment to 180-350 ℃, preferably to 250-270 ℃ before said contacting.
Wherein the heating facilitates evaporation of the solvent (e.g., water) to facilitate attachment of the active ingredient to the carrier.
In a preferred embodiment, in step 2, the active mother liquor is contacted with the support by spraying.
In a further preferred embodiment, in step 2, the spraying is performed at 350 ℃, preferably 200 ℃ and 320 ℃, more preferably 250 ℃ and 300 ℃.
Wherein the active mother liquor is sprayed onto the surface of the carrier.
In a further preferred embodiment, in step 2, the spraying rate is 0.05 to 1mL/min gcat, preferably 0.1 to 0.5mL/min gcat.
In a preferred embodiment, the supported active component is present in an amount of 10% to 30% by weight, based on 100% by weight of the catalyst precursor.
In a further preferred embodiment, the supported active component is present in an amount of from 14% to 18% by weight, based on 100% by weight of the procatalyst.
In a preferred embodiment, a binder and pore-expanding agent are added to the activation mother liquor after step 1 and before step 2, or a binder and pore-expanding agent are added to the catalyst precursor after step 2 and before step 3.
In a further preferred embodiment, the binder is selected from at least one of 704 glue, 705 glue, 706 glue and 708 glue; the pore-expanding agent is selected from at least one of ammonium carbonate, ammonium bicarbonate and ammonium chloride.
In a further preferred embodiment, the binder is used in an amount of 0.5 to 5% by weight of the total mass of the active mother liquor, and the pore-expanding agent is used in an amount of 0.01 to 0.1% by weight of the total mass of the active mother liquor.
The catalyst can fall off in the using process, particularly a certain amount of water is generated in the benzene oxidation process, and in addition, a certain amount of water vapor is also contained in the air, so that the catalyst is easy to fall off and fall off, and the performance of the catalyst is reduced. In addition, in order to better improve and optimize the mass transfer of the catalyst, ammonium carbonate and ammonium bicarbonate are used as pore-enlarging agents in the invention, on one hand, ammonia generated by the decomposition of ammonium carbonate or ammonium bicarbonate is used to form a reducing atmosphere; on the other hand, after the ammonium carbonate or the ammonium bicarbonate is decomposed in the spraying process, vacancies are left for keeping, and pore channels are formed to be beneficial to the diffusion of reactants and products.
In a preferred embodiment, in step 3, the activation treatment is performed in a closed environment in an activation atmosphere selected from nitrogen and/or helium.
Wherein the catalyst is activated in a closed vessel. The closed container is a cylindrical or square activation furnace body, the upper part of the furnace body is sealed by a flange, so that the inner space is isolated from the outside, electric furnace wires are wound around the outer wall of the furnace body, heat-preservation cloth or heat-preservation tiles are arranged outside the electric furnace wires, and the heating temperature of the furnace body is controlled by an automatic digital temperature control meter; the furnace body is equipped with the blow vent from top to bottom, and lower blow vent is as the gas inlet port, goes up the blow vent and as gas outlet, and gaseous velocity of flow is controlled through gas mass flowmeter.
In a further preferred embodiment, in step 3, the activation treatment is carried out as follows:
3.1) heating from room temperature to 150-200 ℃ at a heating rate of 70-150 ℃/h, and keeping for 5-30 minutes;
3.2) raising the temperature to 250 ℃ at the heating rate of 60-120 ℃/h, and keeping the temperature for 5-30 minutes;
3.3) raising the temperature to 350 ℃ at the heating rate of 50-100 ℃/h, and keeping the temperature for 10-60 minutes;
3.4) raising the temperature to 420-480 ℃ at the heating rate of 40-90 ℃/h, and maintaining for 5-10 hours;
3.5) cooling to room temperature at a heating rate of 40-80 ℃/h.
In a still further preferred embodiment, the rate of temperature rise is gradually reduced from step 3.1) to step 3.5).
Wherein, through the mode of reducing the rate of rising temperature gradually, can better protection catalyst, improve catalyst's performance.
The third purpose of the invention is to provide a catalyst for preparing maleic anhydride by benzene oxidation, which is obtained by the preparation method of the second purpose of the invention.
The fourth purpose of the invention is to provide the application of the catalyst for preparing maleic anhydride by benzene oxidation or the catalyst for preparing maleic anhydride by benzene oxidation obtained by the preparation method of the first purpose of the invention in preparing maleic anhydride by benzene oxidation.
In a preferred embodiment, the reaction for preparing maleic anhydride by benzene oxidation is a molten salt circulation reaction, and the temperature of the molten salt is 340-360 ℃.
Wherein a molten salt bath is used for heating and heat removal.
In a preferred embodiment, in the reaction for preparing maleic anhydride by benzene oxidation, maleic anhydride is prepared by oxidizing a mixed gas of benzene and air through a fixed bed reactor filled with the catalyst.
In a further preferred embodiment, the working concentration of benzene in the reaction of oxidizing benzene to prepare maleic anhydride is 40-55g/Nm3。
In a further preferred embodiment, the volume space velocity of the mixed gas is 1500--1Preferably 2000--1。
In a preferred embodiment, the reaction pressure is negative, normal and elevated, preferably normal.
Wherein, a fixed bed reactor is used in the reaction of preparing maleic anhydride by benzene oxidation, and a molten salt bath is adopted for heating and removing heat. In the evaluation reaction process, the temperatures of all positions in the catalyst bed layer from top to bottom are inconsistent, wherein the highest value of the temperature area is called the hot spot temperature of the catalyst, the corresponding bed layer height is the position of the hot spot of the catalyst, and the thermocouple is used for measuring by means of the temperature of the broaching layer. The benzene concentration is the number of grams of benzene contained in a unit volume of air, and a higher number indicates a higher benzene content in air.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nonmetal is used as an auxiliary agent, so that the content of the metal auxiliary agent is reduced or a rare earth metal auxiliary agent is not used, and the cost of the catalyst can be reduced;
(2) the non-metal auxiliary agent boron is adopted, so that the acid strength of the surface of the catalyst can be adjusted, benzene adsorption and maleic anhydride desorption are facilitated, maleic anhydride selectivity is further facilitated, and the performance of the catalyst is further improved.
(3) The active component is fixed by the binder, so that the powder falling and falling of the catalyst are reduced, and the stability of the catalyst is improved.
(4) And the addition of the carbonic acid or ammonium bicarbonate forms a reducing atmosphere, so that the deep oxidation of vanadium is avoided, a certain macroporous structure is formed, the mass transfer process is improved, and the performance of the catalyst is improved.
(5) The performance of the catalyst can be further improved by compounding the non-metal boron and the metal auxiliary agent, combining a binder to fix the active component and using ammonium carbonate or ammonium bicarbonate.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art. The quantitative tests in the following examples, all set up three replicates and the results averaged.
[ example 1 ]
Step 1: dissolving 102g of oxalic acid in 480mL of water at room temperature, adding 67.6g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is dissolved to form a uniform and stable solution; dissolving 28.8g of ammonium molybdate in 70mL of water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.5g of trisodium phosphate, 1.8g of diammonium phosphate, 1.4g of nickel nitrate, 1.2g of boric acid and 1.3g of indium acetate are added in turn under stirring, and after the mother liquor is stirred uniformly, 10g of 705 glue and 2.5g of ammonium carbonate are added.
Step 2: the 330g carrier is put into a stainless steel rotary drum which can rotate and be heated, a thermocouple sleeve is arranged at the bottom of the carrier, and a thermocouple inside the carrier is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotating speed of the rotary drum is adjusted to be 15 r/min, when the temperature of the carrier is heated to 250 ℃, the catalyst active component mixture in a dark green slurry state is sprayed on the carrier through a special nozzle, the spraying speed is 0.08mL/min gcat, the spraying temperature is 280 ℃, the temperature of the carrier is kept at 280 ℃, the catalyst precursor is dried after the spraying is finished, and 398g of the catalyst precursor is obtained by weighing, wherein the weight content of the active substances is 17.1 percent based on the total weight of the catalyst precursor.
And step 3: 180g of the catalyst precursor is placed in an activation furnace, sealed, heated from room temperature to 150 ℃ at a heating rate of 150 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 120 ℃/h for 10 minutes, heated to 350 ℃ at a heating rate of 100 ℃/h for 20 minutes at 350 ℃, heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours at the temperature, and then gradually cooled to room temperature to prepare the catalyst A.
Catalyst a was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
[ example 2 ]
Step 1: dissolving 102g of oxalic acid in 480mL of water at room temperature, adding 67.6g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is dissolved to form a uniform and stable solution; dissolving 28.8g of ammonium molybdate in 70mL of water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.5g of trisodium phosphate, 1.8g of diammonium phosphate, 1.4g of nickel nitrate, 0.2g of boric acid and 1.3g of indium acetate are added in turn under stirring, and after mixing, a catalyst active mother liquor is prepared, and then 10g of 705 glue and 2.5g of ammonium carbonate are added.
Step 2: the 330g carrier is put into a stainless steel rotary drum which can rotate and be heated, a thermocouple sleeve is arranged at the bottom of the carrier, and a thermocouple inside the carrier is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotating speed of the rotary drum is adjusted to be 15 r/min, when the temperature of the carrier is heated to 250 ℃, the catalyst active component mixture in the form of dark green slurry is sprayed on the carrier through a special nozzle, the spraying speed is 0.08mL/min gcat, the spraying temperature is 280 ℃, the temperature of the carrier is kept at 280 ℃, after the spraying is finished, the catalyst precursor is dried, and 396g of catalyst precursor is obtained by weighing, wherein the content of the active substance is 16.7 percent based on the total mass of the catalyst precursor.
And C: 180g of the catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 150 ℃ at a heating rate of 150 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 120 ℃/h for 10 minutes, heated to 350 ℃ at a heating rate of 100 ℃/h for 20 minutes at 350 ℃, heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature to obtain catalyst B.
Catalyst B was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
[ example 3 ]
Step 1: dissolving 102g of oxalic acid in 480mL of water at room temperature, adding 67.6g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is dissolved to form a uniform and stable solution; dissolving 28.8g of ammonium molybdate in 70mL of water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.5g of trisodium phosphate, 1.8g of diammonium phosphate, 1.4g of nickel nitrate, 1.2g of boric acid and 1.0g of antimony trichloride are added in turn under stirring, and after mixing, a catalyst active mother liquor is prepared, and then 10g of 705 glue and 2.0g of ammonium bicarbonate are added.
Step 2: the 330g carrier is put into a stainless steel rotary drum which can rotate and be heated, a thermocouple sleeve is arranged at the bottom of the carrier, and a thermocouple inside the carrier is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotating speed of the rotary drum is adjusted to be 15 r/min, when the temperature of the carrier is heated to 250 ℃, the catalyst active component mixture in the form of dark green slurry is sprayed onto the carrier through a special nozzle, the spraying speed is 0.08mL/min gcat, the spraying temperature is 280 ℃, the temperature of the carrier is kept at 280 ℃, after the spraying is finished, the catalyst precursor is dried, and 396g of catalyst precursor is obtained by weighing, wherein the content of active substances is 16.7 percent based on the total mass of the catalyst.
And C: 180g of the catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 150 ℃ at a heating rate of 150 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 120 ℃/h for 10 minutes, heated to 350 ℃ at a heating rate of 100 ℃/h for 20 minutes at 350 ℃, heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature to obtain catalyst C.
Catalyst C was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
[ example 4 ]
Step 1: dissolving 102g of oxalic acid in 480mL of water at room temperature, adding 67.6g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is dissolved to form a uniform and stable solution; dissolving 28.8g of ammonium molybdate in 70mL of water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.5g of trisodium phosphate, 1.8g of diammonium phosphate, 1.4g of nickel nitrate, 0.3g of boric acid and 1.0g of antimony trichloride are added in turn under stirring, and after mixing, a catalyst active mother liquor is prepared, and then 10g of 705 glue and 2.0g of ammonium bicarbonate are added.
Step 2: the 330g carrier is put into a stainless steel rotary drum which can rotate and be heated, a thermocouple sleeve is arranged at the bottom of the carrier, and a thermocouple inside the carrier is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotating speed of the rotary drum is adjusted to be 15 r/min, when the temperature of the carrier is heated to 250 ℃, the catalyst active component mixture in the form of dark green slurry is sprayed on the carrier through a special nozzle, the spraying speed is 0.08mL/min gcat, the spraying temperature is 280 ℃, the temperature of the carrier is kept at 280 ℃, the catalyst precursor is dried after the spraying is finished, and 395g of the catalyst precursor is obtained by weighing, wherein the content of active substances is 16.5 percent based on the total mass of the catalyst.
And step 3: 180g of the above catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 150 ℃ at a heating rate of 150 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 120 ℃/h for 10 minutes, heated to 350 ℃ at a heating rate of 100 ℃/h for 20 minutes at 350 ℃, then heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours at the temperature, and then gradually cooled to room temperature to obtain catalyst D.
Catalyst D was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
[ example 5 ]
Step 1: dissolving 102g of oxalic acid in 480mL of water at room temperature, adding 67.6g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is dissolved to form a uniform and stable solution; dissolving 28.8g of ammonium molybdate in 70mL of water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.5g of trisodium phosphate, 1.8g of diammonium phosphate, 1.4g of nickel nitrate, 1.2g of boric acid and 1.0g of bismuth nitrate are added in turn under stirring, and the mixture is mixed to prepare the active mother liquor of the catalyst.
Step 2: the 330g carrier is put into a stainless steel rotary drum which can rotate and be heated, a thermocouple sleeve is arranged at the bottom of the carrier, and a thermocouple inside the carrier is connected with a temperature display instrument to display the temperature change in the spraying process in real time. Adjusting the rotating speed of a rotary drum to 15 revolutions per minute, when the temperature of the carrier is heated to 250 ℃, spraying the catalyst active component mixture in a dark green slurry state onto the carrier through a special nozzle, wherein the spraying speed is 0.08mL/min gcat, the spraying temperature is 280 ℃, keeping the temperature of the carrier at 280 ℃, drying the catalyst precursor after the spraying is finished, weighing to obtain 397g of the catalyst precursor, and adding 12g of 705 glue and 2.0g of ammonium bicarbonate, wherein the content of the active substances is 16.9 percent of the total mass of the catalyst.
And step 3: 180g of the catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 150 ℃ at a heating rate of 150 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 120 ℃/h for 10 minutes, heated to 350 ℃ at a heating rate of 100 ℃/h for 20 minutes at 350 ℃, heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature to obtain catalyst E.
Catalyst E was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
[ example 6 ]
Step 1: dissolving 102g of oxalic acid in 480mL of water at room temperature, adding 67.6g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is dissolved to form a uniform and stable solution; dissolving 28.8g of ammonium molybdate in 70mL of water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.5g of trisodium phosphate, 1.8g of diammonium phosphate, 1.4g of nickel nitrate, 0.3g of boric acid and 1.0g of bismuth nitrate are added in turn under stirring, and after mixing, a catalyst active mother liquor is prepared, and then 12g of 705 glue and 2.0g of ammonium bicarbonate are added.
Step 2: the 330g carrier is put into a stainless steel rotary drum which can rotate and be heated, a thermocouple sleeve is arranged at the bottom of the carrier, and a thermocouple inside the carrier is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotating speed of the rotary drum is adjusted to be 15 r/min, when the temperature of the carrier is heated to 250 ℃, the catalyst active component mixture in the form of dark green slurry is sprayed on the carrier through a special nozzle, the spraying speed is 0.08mL/min gcat, the spraying temperature is 280 ℃, the temperature of the carrier is kept between 280 ℃, after the spraying is finished, the catalyst precursor is dried and weighed to obtain 395g of catalyst precursor, and the content of active substances is 16.5 percent based on the total mass of the catalyst.
And step 3: 180g of the catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 150 ℃ at a heating rate of 150 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 120 ℃/h for 10 minutes, heated to 350 ℃ at a heating rate of 100 ℃/h for 20 minutes at 350 ℃, heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours at the temperature, and then gradually cooled to room temperature to obtain catalyst F.
Catalyst F was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃ and the results are shown in Table 1.
[ example 7 ]
The procedure of example 1 was repeated except that: replacing 1.3g of indium acetate with 0.4g of antimony trichloride and 0.9g of indium acetate; catalyst G was obtained.
Catalyst G was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
[ example 8 ]
The procedure of example 3 was repeated except that: replacing 1.0g of antimony trichloride with 0.5g of antimony trichloride and 0.5g of bismuth nitrate; catalyst H was obtained.
Catalyst H was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
[ example 9 ]
The procedure of example 1 was repeated except that: replacing 1.3g of indium acetate with 0.3g of indium acetate and 1.0g of bismuth nitrate; catalyst I is obtained.
Catalyst I was loaded into the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
Comparative example 1
Catalyst J was prepared in the same manner as in example 1, except that only 1.2g of boric acid was added as an auxiliary compound, and no indium acetate was added. After the spraying and drying treatment, a catalyst precursor of 397 was obtained, the active material content being 16.9% by mass of the total catalyst.
Catalyst J was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
Comparative example 2
Catalyst K was prepared in the same manner as in example 1, except that only 1.3g of indium acetate was added as the auxiliary compound. After the spraying and drying treatment, a catalyst precursor of 395 was obtained, having an active material content of 16.5% by mass based on the total mass of the catalyst.
Catalyst K was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃, the results are shown in table 1.
Comparative example 3
Catalyst K was prepared in the same manner as in example 7 except that boric acid was not used to obtain catalyst L.
The catalyst L was loaded in the fixed bed reactor and tested using a molten salt temperature of 352 ℃ and the results are shown in Table 1.
[ Experimental example ]
The catalyst activated by the activation furnace is filled in a 120mL bubbling molten salt circulating reactor, the bottom of the reactor is supported by an inert carrier, the middle of the reactor is filled with 120mL catalyst, and the upper part of the reactor is filled with the inert carrier with a certain height. When the molten salt is heated to the temperature required by the reaction, air is supplied, benzene is simultaneously fed, sampling analysis is started after the benzene concentration reaches the required working condition concentration and is stabilized for 1 hour, and the sampling evaluation results of the catalysts are shown in table 1.
The calculation method of each index is as follows:
benzene conversion (%) — amount of substance of benzene at the inlet of the reactor per unit time-amount of substance of benzene at the outlet of the reactor per unit time)/amount of substance of benzene at the inlet of the reactor per unit time × 100%.
Weight yield (%) of maleic anhydride, benzene conversion × selectivity of maleic anhydride × 98/78 × 100%.
TABLE 1120 mL Single tube Activity evaluation results
Figure BDA0002648977910000171
Figure BDA0002648977910000181
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (15)

1. The catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component comprises a main catalyst and a cocatalyst, and the cocatalyst comprises boron and at least one of indium element, antimony element and bismuth element.
2. The benzene oxidation maleic anhydride preparation catalyst according to claim 1, wherein the loading amount of the active component is 10-20%, preferably 14-18%, based on the catalyst.
3. The benzene oxidation maleic anhydride catalyst according to claim 1 or 2,
the carrier is selected from at least one of silicon carbide, alumina and silicon dioxide; and/or
The main catalyst comprises vanadium element, molybdenum element, sodium element, phosphorus element and nickel element.
4. The catalyst for producing maleic anhydride by oxidation of benzene as claimed in claim 3, wherein the molar ratio of the vanadium element, the molybdenum element, the sodium element, the phosphorus element, the nickel element, the boron element and the M element is 1 (0.2-0.90): 0.001-0.2): 0.005-0.25): 0.0001-0.05): 0.001-0.06): 0.0001-0.05, wherein V is the number of V, respectively2O5Calculated in mol as MoO3In terms of molar amount, as Na2Molar amount of O in P2O5Calculated as molar amount, calculated as molar amount of NiO, calculated as B2O3The molar amount is calculated by the molar amount of the M element.
5. A method for preparing the catalyst for preparing maleic anhydride by benzene oxidation according to any one of claims 1 to 4, comprising the steps of:
step 1, adding a compound containing an active component into a reducing agent solution to obtain an active mother liquor;
step 2, contacting the active mother liquor with a carrier, and drying to obtain a catalyst precursor;
and 3, activating the catalyst precursor to obtain the maleic anhydride catalyst prepared by benzene oxidation.
6. The method of claim 5, wherein the active component-containing compound comprises a procatalyst compound and a cocatalyst compound;
preferably, the main catalyst compound includes a vanadium compound, a molybdenum compound, a sodium compound, a phosphorus compound, and a nickel compound; and/or the promoter compound comprises a boron-containing compound and a M-containing compound, M being selected from at least one of indium, antimony and bismuth.
7. The production method according to claim 6,
the vanadium compound is selected from at least one of ammonium metavanadate, vanadyl oxalate, vanadium pentoxide and sodium vanadate; and/or
The molybdenum compound is at least one selected from ammonium molybdate, molybdenum trioxide and calcium molybdate, and is preferably ammonium molybdate; and/or
The sodium compound is selected from at least one of sodium dihydrogen phosphate and trisodium phosphate, preferably trisodium phosphate; and/or
The phosphorus compound is at least one selected from ammonium dihydrogen phosphate, 85-115% phosphoric acid and phosphorus pentoxide, and is preferably ammonium dihydrogen phosphate; and/or
The nickel compound is at least one selected from nickel nitrate, nickel sulfate, nickel chloride and nickel oxide, and is preferably nickel nitrate.
8. The production method according to claim 6,
the boron-containing compound is selected from at least one of boric acid, boric oxide and sodium borate; and/or
The M-containing compound is selected from at least one of soluble salts of M-containing elements, preferably at least one of acetate, nitrate and chloride of the M-containing elements.
9. The method according to claim 6, wherein the ratio of the vanadium compound to the molybdenum compound: the molar ratio of the sodium compound, the phosphorus compound, the nickel compound, the boron-containing compound and the M-containing compound is 1 (0.2-0.90): 0.001-0.2): 0.005-0.25): 0.0001-0.05): 0.001-0.06): 0.0001-0.05, wherein V is respectively used2O5Calculated in mol as MoO3In terms of molar amount, as Na2Molar amount of O in P2O5Calculated as molar amount, calculated as molar amount of NiO, calculated as B2O3The molar amount is calculated by the molar amount of the M element.
10. The production method according to claim 5,
in the step 1, the reducing agent is selected from oxalic acid, preferably, the molar ratio of the used amount of the reducing agent to the vanadium compound is (1-3): 1, preferably (1.5-2.5): 1; and/or
In step 2, before the contacting, the carrier is heated to 180-350 ℃, preferably to 250-270 ℃; and/or
The active mother liquor is contacted with the carrier in a spraying mode; preferably, the spraying is carried out at 150-350 ℃, preferably 200-320 ℃; more preferably, the spray rate is from 0.05 to 1mL/min gcat.
11. The process according to claim 5, characterized in that the supported active component is present in an amount of 10% to 30%, preferably 14% to 18%, by weight, based on 100% by weight of the procatalyst.
12. The preparation method according to any one of claims 5 to 11, wherein a binder and a pore-expanding agent are added to the active mother liquor after step 1 and before step 2, or a binder and a pore-expanding agent are added to the catalyst precursor after step 2 and before step 3;
preferably, the binder is selected from at least one of 704 glue, 705 glue, 706 glue and 708 glue; and/or the pore-expanding agent is selected from at least one of ammonium carbonate, ammonium bicarbonate and ammonium chloride;
more preferably, the binder accounts for 0.5-5% of the total mass of the active mother liquor, and the pore-expanding agent accounts for 0.01-0.1% of the total mass of the active mother liquor.
13. The method according to claim 12, wherein in step 3, the activation treatment is performed in a closed environment in an activation atmosphere selected from nitrogen and/or helium;
preferably, the activation treatment is performed as follows:
3.1) heating from room temperature to 150-200 ℃ at a heating rate of 70-150 ℃/h, and keeping for 5-30 minutes;
3.2) raising the temperature to 250 ℃ at the heating rate of 60-120 ℃/h, and keeping the temperature for 5-30 minutes; 3.3) raising the temperature to 350 ℃ at the heating rate of 50-100 ℃/h, and keeping the temperature for 10-60 minutes; 3.4) raising the temperature to 420-480 ℃ at the heating rate of 40-90 ℃/h, and maintaining for 5-10 hours; 3.5) cooling to room temperature at a heating rate of 40-80 ℃/h.
14. The catalyst for preparing maleic anhydride through benzene oxidation, which is obtained by the preparation method of any one of claims 5 to 13.
15. Use of the catalyst for maleic anhydride production by benzene oxidation according to any one of claims 1 to 4 or the catalyst for maleic anhydride production by benzene oxidation obtained by the production method according to any one of claims 5 to 13 for maleic anhydride production by benzene oxidation;
preferably, the reaction for preparing maleic anhydride by benzene oxidation is a molten salt circulating reaction, and the temperature of the molten salt is 340-360 ℃; and/or, oxidizing and preparing maleic anhydride by using mixed gas of benzene and air through a fixed bed reactor filled with the catalyst, wherein the preferable working condition concentration of the benzene is 40-55g/Nm3。
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CN107774287A (en) * 2016-08-29 2018-03-09 中国石油化工股份有限公司 A kind of loaded catalyst and its preparation for benzene oxidatoin cis-butenedioic anhydride
CN109201095A (en) * 2017-07-04 2019-01-15 中国石油化工股份有限公司 A kind of benzene oxidatoin catalyst for preparing cis-anhydride and the preparation method and application thereof
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US3947474A (en) * 1972-10-24 1976-03-30 Halcon International, Inc. Catalyst and use thereof
US4118402A (en) * 1974-12-02 1978-10-03 Nippon Shokubai Kagaku Kogyo Co., Ltd. Preparation of maleic anhydride
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