CN114100651B - Catalyst for preparing maleic anhydride by benzene oxidation and preparation method and application thereof - Google Patents

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

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CN114100651B
CN114100651B CN202010863579.XA CN202010863579A CN114100651B CN 114100651 B CN114100651 B CN 114100651B CN 202010863579 A CN202010863579 A CN 202010863579A CN 114100651 B CN114100651 B CN 114100651B
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catalyst
compound
maleic anhydride
molar amount
benzene
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CN114100651A (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 maleic anhydride catalyst prepared by benzene oxidation and a preparation method and application thereof. The invention adopts the nonmetal auxiliary agent boron, and can adjust the acid strength of the surface of the catalyst, thereby being beneficial to benzene adsorption and maleic anhydride desorption, and being more beneficial to improving the maleic anhydride selectivity, and further improving the catalyst performance. Meanwhile, the non-metal boron and the metal auxiliary agent are compounded, and the active components are fixed by combining with the binder, and the performance of the catalyst can be further improved by using ammonium carbonate or ammonium bicarbonate.

Description

Catalyst for preparing maleic anhydride by 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 next to phthalic anhydride. The main application of the catalyst is very wide, and the catalyst 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 raw materials of medicines and pesticides. Unsaturated Polyester Resins (UPR) are the largest consumer products downstream of maleic anhydride, and secondly 1, 4-butanediol, both of which can be consumed in amounts of more than 60% of the total maleic anhydride consumed.
The production process of maleic anhydride can be classified into benzene and n-butane method according to the kinds of raw materials. In recent years, the capacity of the device for oxidizing n-butane in China is continuously enlarged, the development trend is faster, but the process for preparing maleic anhydride by the n-butane is more complex than that by using benzene, and the operation is relatively difficult, so that the process using benzene as a raw material can still account for 50% of the total capacity of maleic anhydride. In addition, since 2019, as the price of maleic anhydride goes down, the price of benzene also gradually decreases, but the price of n-butane is not greatly changed, at present, the market price of n-butane is 4000 yuan/ton, the price of benzene is 4500 yuan/ton, the price difference between the benzene and the n-butane is very small, when the price difference between raw material benzene and the ton price of n-butane is within 1500 yuan by combining the operation cost of benzene method and butane maleic anhydride device, the comprehensive cost advantage of benzene method is higher than that of n-butane method.
In the areas with relatively abundant coal resources and relatively deficient petroleum resources, such as inland areas of Shanxi province, maleic anhydride devices which adopt coked benzene as raw materials still have very large productivity due to the fact that a large amount of coked benzene is produced as a byproduct. At present, due to the fact that the original cost and the price difference of maleic anhydride products are small, great competition exists in the production of enterprises, in order to improve the economic benefit, the production cost is reduced as much as possible, the raw material cost of benzene occupies more than 80% of the production cost of maleic anhydride, the benzene consumption is reduced, the byproducts of benzene are reduced, the selectivity of maleic anhydride is improved, and the utilization rate of benzene is improved, so that the economic benefit can be remarkably improved.
The current patent of maleic anhydride catalyst by benzene oxidation is mainly focused on screening metal auxiliary agents and optimizing the formula, for example, patent CN103816931A proposes a preparation method of maleic anhydride catalyst by benzene oxidation, which comprises the steps of dissolving molybdenum compounds and vanadium compounds in hydrochloric acid, adding solution containing phosphorus, sodium, nickel, copper and other compounds into the active hydrochloric acid, spraying the obtained solution on an inert talcum ceramic carrier, and activating at 350-450 ℃ in inert gas atmosphere to obtain the active catalyst. Hydrochloric acid is a very volatile and corrosive acid, which not only causes corrosion of equipment and increases equipment cost, but also damages the health of workers and causes a series of problems such as environmental pollution.
The 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 auxiliary agent, for example, one or more of lanthanum, cerium, terbium, europium and other elements, silicon carbide as a carrier and adopting an impregnation method or a spraying method.
Currently, published patents focus on the study of metal promoters, especially rare earth promoters, and relatively little on nonmetallic promoters, patent CN101284242a teaches that the appropriate addition of P to the catalyst 2 O 5 The method has the advantages that the acidity of the catalyst can be increased, the adsorption of benzene is facilitated, and the desorption of products is facilitated, so that the deep oxidation of benzene can be reduced, more maleic anhydride generation reactions are facilitated, based on the thought, a nonmetal auxiliary agent is adopted, meanwhile, no rare earth metal auxiliary agent is added, the acid strength of the catalyst is further reduced after the catalyst is prepared by the method, and the selectivity of maleic anhydride is further improved under the condition that the activity is kept at a higher level.
Disclosure of Invention
Benzene oxidation maleic anhydride preparation reaction belongs to gas-solid phase reaction, wherein benzene adsorption and maleic anhydride adsorption play a very important role in the reaction process, the benzene adsorption and maleic anhydride desorption time is too long, deep oxidation is easy, and the products mainly comprise carbon dioxide and carbon monoxide. It is found that the acid center plays a very important role in the adsorption and desorption of benzene, but the acid center cannot be too strong, and if the acid center is too strong, the benzene adsorption and the maleic anhydride desorption are too long, and are easy to deeply oxidize under the action of lattice oxygen, so that the maleic anhydride selectivity is reduced. Therefore, the regulation of the strength of the acid center is very critical for improving the performance of the catalyst.
In order to overcome the problems in the prior art, the present invention provides a catalyst for preparing maleic anhydride by benzene oxidation, which is introduced with a boron-containing compound in the preparation of the catalyst, and the inventors have found that boron is an element for regulating acidity, and when boron is supported or doped into the catalyst, particularly in an oxide catalyst, sp can be generated 3 The orbit is hybridized, so that a tetrahedrally coordinated framework boric acid center is formed, the acidity is weak, and the boric acid center is a weak acid center, which is favorable for benzene adsorption and maleic anhydride desorption, therefore, the invention adopts boron as one of auxiliary agents to improve the selectivity of maleic anhydride.
One of the purposes of the invention is to provide a maleic anhydride catalyst prepared by benzene oxidation, which 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, antimony and bismuth.
According to research, at least one of the three elements of indium, antimony and bismuth is used as a metal auxiliary agent, and has obvious promotion effect on improving the selectivity of the catalyst, so that the invention adopts the compatibility of nonmetallic element boron and metallic elements of indium, antimony and bismuth, and the selectivity of the catalyst is improved together through the synergistic effect of boron and the metals, so that the better maleic anhydride weight yield is obtained, and the maleic anhydride weight yield can reach 100% under the evaluation condition.
The invention aims to solve the problem of low maleic anhydride selectivity in the prior art, adopts boron to adjust the acid strength of the catalyst, adopts a metal auxiliary agent to further improve the maleic anhydride selectivity, and jointly improves the performance of the catalyst under the compatibility of a 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 carrier is in the shape of any one of a sphere, a cylinder, a ring, a clover.
In a preferred embodiment, the loading of the active component therein is from 10% to 20%, preferably from 14 to 18%, based on the catalyst.
Wherein, the insufficient loading of active components can affect the activity of the catalyst, the too low benzene conversion rate, the too high loading of active components, the serious deep oxidation of the catalyst, more byproducts and the weight yield reduction of maleic anhydride.
In a preferred embodiment, the main catalyst comprises 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, calcium molybdate, preferably ammonium molybdate.
In a preferred embodiment, the sodium element is at least one of sodium dihydrogen phosphate and trisodium phosphate, preferably trisodium phosphate.
In a preferred embodiment, the phosphorus element is derived from at least one of monoammonium phosphate, 85% -115% phosphoric acid, phosphorus pentoxide, preferably monoammonium phosphate.
In a preferred embodiment, the nickel element is at least one of nickel nitrate, nickel sulfate, nickel chloride, nickel oxide, preferably nickel nitrate.
In a preferred embodiment, the boron element is derived from at least one of boric acid, boron oxide and sodium borate.
In a preferred embodiment, the indium element, antimony element and bismuth element are derived from at least one of soluble salts containing the elements.
In a further preferred embodiment, the indium element, antimony element and bismuth element are derived from at least one of acetate, nitrate and chloride salts 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 the group consisting of an indium element, an antimony element, and a boron element, or selected from the group consisting of an antimony element, a bismuth element, and a boron element). Wherein the molar ratio of the two metal elements is between (0.01-100): 1, preferably between (0.1-20): 1, more preferably between (0.1-10): 1, for example between (0.1-5): 1.
The inventors have found through a large number of experiments that when at least two elements selected from the group consisting of indium element, antimony element and bismuth element, the effect is remarkable due to the selection of one of them.
In a preferred embodiment, the molar ratio of vanadium element, molybdenum element, sodium element, phosphorus element, nickel element, boron element and 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 respectively 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, calculated as NiO molar amount, calculated as B 2 O 3 Molar amount, based on the molar amount of M element, when M is selected from the two co-metals, M is calculated as the sum of the molar amounts of the two co-metals.
In a further preferred embodiment, the molar ratio of vanadium element, molybdenum element, sodium element, phosphorus element, nickel element, boron element and M element is 1 (0.3-0.80): (0.01-0.1): (0.01-0.1): (0.005-0.03): (0.002-0.02): (0.005-0.02), wherein V is respectively 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, calculated as NiO molar amount, calculated as B 2 O 3 Molar amount, based on the molar amount of M element, when M is selected from the two co-metals, M is calculated as the sum of the molar amounts of the two co-metals.
The second purpose of the invention is to provide a preparation method of the maleic anhydride catalyst prepared by benzene oxidation, which comprises the following steps:
step 1, adding a compound containing an active component into a reducer solution to obtain an active mother solution;
step 2, the active mother liquor is contacted with a carrier, and a catalyst precursor is obtained through drying;
and step 3, performing activation treatment on the catalyst precursor to obtain the maleic anhydride catalyst prepared by benzene oxidation.
In a preferred embodiment, the active component-containing compound comprises 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 phosphorus compound, and a nickel compound.
In a still further preferred embodiment, the promoter compound comprises a boron-containing compound and an 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 sodium dihydrogen 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, nickel oxide, preferably nickel nitrate.
In a preferred embodiment, the boron-containing compound is selected from at least one of boric acid, boron oxide and sodium borate.
In a preferred embodiment, the M-containing compound is selected from at least one of the soluble salts containing an M element.
In a further preferred embodiment, the M element is derived from at least one of acetate, nitrate, chloride salt containing the M element.
In a preferred embodiment, the molar ratio of 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 respectively 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, calculated as NiO molar amount, calculated as B 2 O 3 Molar amount, based on the molar amount of M element, when M is selected from the two co-metals, M is calculated as the sum of the molar amounts of the two co-metals.
In a further preferred embodiment, the vanadium compound, molybdenum compound, sodium compound, phosphorus compound, nickel compound, boron-containing compoundThe molar ratio of the compound to the M-containing compound is 1 (0.3-0.80): (0.01-0.1): (0.01-0.1): (0.005-0.03): (0.002-0.02): (0.005-0.02), wherein V is respectively 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, calculated as NiO molar amount, calculated as B 2 O 3 Molar amount, based on the molar amount of M element, when M is selected from the two co-metals, M is calculated as the sum of the molar amounts of the two co-metals.
The invention aims to solve the problem of low maleic anhydride selectivity in the prior art, adopts boron to adjust the acid strength of the catalyst, adopts a metal auxiliary agent M to further improve the maleic anhydride selectivity, and jointly improves the performance of the catalyst under the compatibility of a 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 step 1, the molar ratio of the reducing agent to the vanadium compound is (1 to 3): 1, preferably (1.5 to 2.5): 1.
In a preferred embodiment, in step 2, the support is subjected to a heat treatment to 180-350 ℃, preferably to 250-270 ℃, prior to said contacting.
Wherein the heating facilitates the volatilization of the solvent (e.g., water) and promotes the attachment of the active ingredient to the carrier.
In a preferred embodiment, in step 2, the active mother liquor is contacted with the support in a spray-on manner.
In a further preferred embodiment, in step 2, the spraying is performed at 150-350 ℃, preferably 200-320 ℃, more preferably 250-300 ℃.
Wherein the active mother liquor is sprayed onto the surface of the carrier.
In a still further preferred embodiment, in step 2, the spraying speed is from 0.05 to 1mL/min gcat, preferably from 0.1 to 0.5mL/min gcat.
In a preferred embodiment, the active component is supported in an amount of 10% to 30% by weight, based on 100% by weight of the catalyst precursor.
In a further preferred embodiment, the active component is supported in an amount of 14% to 18% by weight, based on 100% by weight of the catalyst precursor.
In a preferred embodiment, the binder and pore-expanding agent are added to the active mother liquor after step 1, before step 2, or to the catalyst precursor after step 2, before step 3.
In a further preferred embodiment, the adhesive is selected from at least one of 704 glue, 705 glue, 706 glue and 708 glue; the pore-expanding agent is at least one selected from ammonium carbonate, ammonium bicarbonate and ammonium chloride.
In a still further preferred embodiment, the binder is present in an amount of 0.5 to 5% by weight of the total active mother liquor and the pore-expanding agent is present in an amount of 0.01 to 0.1% by weight of the total active mother liquor.
In the invention, a mode of adding a binder is adopted, so that active components are better fixed, and the loss of the active components is prevented. In addition, in order to better improve and optimize the mass transfer of the catalyst, the invention adopts ammonium carbonate and ammonium bicarbonate as pore-expanding agents, and on one hand, ammonia gas generated by decomposing the ammonium carbonate or the ammonium bicarbonate is utilized to form a reducing atmosphere; on the other hand, after the ammonium carbonate or ammonium bicarbonate is decomposed in the spraying process, vacancies are reserved, and pore channels are formed, so that the diffusion of reactants and products is facilitated.
In a preferred embodiment, in step 3, the activation treatment is carried out in a closed environment in an activating 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 through a flange, 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 through an automatic digital temperature control meter; the furnace body is provided with a vent from top to bottom, the lower vent is used as a gas inlet, the upper vent is used as a gas outlet, and the flow rate of gas is controlled by a gas mass flowmeter.
In a further preferred embodiment, in step 3, the activation treatment is performed as follows:
3.1 Raising the temperature 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 220-250 ℃ at a heating rate of 60-120 ℃/h, and keeping for 5-30 minutes;
3.3 Raising the temperature to 300-350 ℃ at a heating rate of 50-100 ℃/h, and keeping for 10-60 minutes;
3.4 Raising the temperature to 420-480 ℃ at a heating rate of 40-90 ℃/h, and maintaining for 5-10 hours;
3.5 And cooling to room temperature at a heating rate of 40-80 ℃/h.
In a still further preferred embodiment, the rate of temperature increase gradually decreases from step 3.1) to step 3.5).
Wherein, through the mode of gradually reducing the rate of temperature rise, the catalyst can be better protected, the performance of catalyst is improved.
The third object of the present invention is to provide a catalyst for preparing maleic anhydride by oxidation of benzene obtained by the second object of the present 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 second purpose of the invention in preparing maleic anhydride by benzene oxidation.
In a preferred embodiment, the benzene oxidation maleic anhydride reaction is a molten salt recycle reaction, and the molten salt temperature is 340-360 ℃.
Wherein, a molten salt bath is adopted for heating and removing heat.
In a preferred embodiment, maleic anhydride is prepared by oxidizing a mixed gas of benzene and air in a fixed bed reactor filled with the catalyst in a benzene oxidation reaction to maleic anhydride.
In a further preferred embodiment, the working concentration of benzene in the reaction for the oxidation of benzene to maleic anhydride is 40-55g/Nm 3 。
In a still further preferred embodiment, the volume space velocity of the mixed gas is 1500 to 3000h -1 Preferably 2000-2500h -1 。
In a preferred embodiment, the reaction pressure is negative, normal and pressurized, 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 the catalyst beds are inconsistent from top to bottom, wherein the highest value of the temperature area is called the hot spot temperature of the catalyst, and the corresponding bed height is the hot spot position of the catalyst. The benzene concentration refers to the number of grams of benzene contained in a unit volume of air, and the higher the number, the higher the benzene content in the air.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give 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 non-metal is adopted as the auxiliary agent, so that the content of the metal auxiliary agent is reduced or the rare earth metal auxiliary agent is not used, and the cost of the catalyst can be reduced;
(2) The nonmetal auxiliary agent boron is adopted, so that the acid strength of the surface of the catalyst can be adjusted, thereby being beneficial to benzene adsorption and maleic anhydride desorption, being more beneficial to improving maleic anhydride selectivity, and further improving the performance of the catalyst.
(3) And the active components are fixed by adopting the adhesive, so that the powder falling and falling of the catalyst are reduced, and the stability of the catalyst is improved.
(4) And adding the carbon amino acid or ammonium bicarbonate to form a reducing atmosphere, avoiding the deep oxidation of vanadium, forming a certain macroporous structure, improving the mass transfer process and improving the performance of the catalyst.
(5) The catalyst can be further improved by adopting the combination of nonmetallic boron and metal auxiliary agent, the combination of the adhesive to fix the active components and the use of ammonium carbonate or ammonium bicarbonate.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are 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, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art. The quantitative tests in the following examples were all set up in triplicate and the results averaged.
[ example 1 ]
Step 1: 102g of oxalic acid is dissolved in 480mL of water at room temperature, 67.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, so as to form a uniform and stable solution; 28.8g of ammonium molybdate is dissolved in 70mL of water to be uniformly dissolved, and the solution is added into the ammonium metavanadate solution; under stirring, sequentially adding 4.5g of trisodium phosphate, 1.8g of diammonium hydrogen phosphate, 1.4g of nickel nitrate, 1.2g of boric acid and 1.3g of indium acetate, mixing to obtain a catalyst active mother solution, and after the mother solution is uniformly stirred, adding 10g of 705 glue and 2.5g of ammonium carbonate.
Step 2: 330g of carrier is put into a rotary stainless steel drum which can be rotated and heated, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotating speed of the rotating drum is regulated to 15 revolutions per minute, when the temperature of the carrier is heated to 250 ℃, the blackish green slurry active component mixture is sprayed on the carrier through a special nozzle, the spraying speed is 0.08mL/min gcat, the spraying temperature is 280 ℃, the carrier temperature is kept at 280 ℃, after the spraying is finished, the catalyst precursor is dried, 398g of catalyst precursor is weighed, and the weight content of active substances is 17.1 percent based on the total weight of the catalyst precursor.
Step 3: 180g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst A.
Catalyst a was charged into the fixed bed reactor and tested using molten salt at 352 ℃ and the results are shown in table 1.
[ example 2 ]
Step 1: 102g of oxalic acid is dissolved in 480mL of water at room temperature, 67.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, so as to form a uniform and stable solution; 28.8g of ammonium molybdate is dissolved in 70mL of water to be uniformly dissolved, and the solution is added into the ammonium metavanadate solution; 4.5g of trisodium phosphate, 1.8g of diammonium hydrogen phosphate, 1.4g of nickel nitrate, 0.2g of boric acid and 1.3g of indium acetate are sequentially added under stirring, a catalyst active mother solution is prepared after mixing, and then 10g of 705 glue and 2.5g of ammonium carbonate are added.
Step 2: 330g of carrier is put into a rotary stainless steel drum which can be rotated and heated, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the rotating drum is regulated to 15 revolutions per minute, 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 carrier temperature is kept at 280 ℃, after the spraying is finished, the catalyst precursor is dried, and 396g of catalyst precursor is weighed, wherein the content of active substances is 16.7 percent based on the total mass of the catalyst precursor.
Step C: 180g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst B.
Catalyst B was packed in the fixed bed reactor and tested using molten salt at 352 ℃ and the results are shown in table 1.
[ example 3 ]
Step 1: 102g of oxalic acid is dissolved in 480mL of water at room temperature, 67.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, so as to form a uniform and stable solution; 28.8g of ammonium molybdate is dissolved in 70mL of water to be uniformly dissolved, and the solution is added into the ammonium metavanadate solution; under stirring, adding sequentially 4.5g trisodium phosphate, 1.8g diammonium phosphate, 1.4g nickel nitrate, 1.2g boric acid and 1.0g antimony trichloride, mixing to obtain a catalyst active mother liquor, and then adding 10g 705 glue and 2.0g ammonium bicarbonate.
Step 2: 330g of carrier is put into a rotary stainless steel drum which can be rotated and heated, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the rotating drum is regulated to 15 revolutions per minute, 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, 396g of catalyst precursor is weighed, and the content of active substances is 16.7 percent based on the total mass of the catalyst.
Step C: 180g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst C.
Catalyst C was packed in the fixed bed reactor and tested using molten salt at 352℃ and the results are shown in table 1.
[ example 4 ]
Step 1: 102g of oxalic acid is dissolved in 480mL of water at room temperature, 67.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, so as to form a uniform and stable solution; 28.8g of ammonium molybdate is dissolved in 70mL of water to be uniformly dissolved, and the solution is added into the ammonium metavanadate solution; under stirring, adding sequentially 4.5g trisodium phosphate, 1.8g diammonium phosphate, 1.4g nickel nitrate, 0.3g boric acid and 1.0g antimony trichloride, mixing to obtain a catalyst active mother liquor, and then adding 10g 705 glue and 2.0g ammonium bicarbonate.
Step 2: 330g of carrier is put into a rotary stainless steel drum which can be rotated and heated, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the rotating drum is regulated to 15 revolutions per minute, 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 carrier temperature is kept at 280 ℃, after the spraying is finished, the catalyst precursor is dried, 395g of catalyst precursor is weighed, and the content of active substances is 16.5 percent based on the total mass of the catalyst.
Step 3: 180g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst D.
Catalyst D was packed in the fixed bed reactor and tested using molten salt at 352 ℃ and the results are shown in table 1.
[ example 5 ]
Step 1: 102g of oxalic acid is dissolved in 480mL of water at room temperature, 67.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, so as to form a uniform and stable solution; 28.8g of ammonium molybdate is dissolved in 70mL of water to be uniformly dissolved, and the solution is added 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 sequence under stirring, and the mixture is mixed to prepare a catalyst active mother liquor.
Step 2: 330g of carrier is put into a rotary stainless steel drum which can be rotated and heated, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotating speed of the rotating drum is regulated to 15 revolutions per minute, 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 between 280 ℃, after the spraying is finished, the catalyst precursor is dried, 397g of the catalyst precursor is weighed, the content of active substances is 16.9 percent based on the total mass of the catalyst, and then 12g of 705 glue and 2.0g of ammonium bicarbonate are added.
Step 3: 180g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst E.
Catalyst E was packed in the fixed bed reactor and tested using molten salt at 352℃and the results are shown in Table 1.
[ example 6 ]
Step 1: 102g of oxalic acid is dissolved in 480mL of water at room temperature, 67.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, so as to form a uniform and stable solution; 28.8g of ammonium molybdate is dissolved in 70mL of water to be uniformly dissolved, and the solution is added into the ammonium metavanadate solution; under stirring, adding sequentially 4.5g trisodium phosphate, 1.8g diammonium phosphate, 1.4g nickel nitrate, 0.3g boric acid and 1.0g bismuth nitrate, mixing to obtain a catalyst active mother liquor, and then adding 12g 705 glue and 2.0g ammonium bicarbonate.
Step 2: 330g of carrier is put into a rotary stainless steel drum which can be rotated and heated, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the rotating drum is regulated to 15 revolutions per minute, 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, 395g of catalyst precursor is weighed, and the content of active substances is 16.5 percent based on the total mass of the catalyst.
Step 3: 180g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst F.
Catalyst F was packed in the fixed bed reactor and tested using molten salt at 352 ℃ and the results are shown in table 1.
[ example 7 ]
The procedure of example 1 was repeated, except that: 1.3g of indium acetate was replaced with 0.4g of antimony trichloride and 0.9g of indium acetate; catalyst G was obtained.
Catalyst G was packed in the fixed bed reactor and tested using molten salt at 352 ℃ and the results are shown in table 1.
[ example 8 ]
The procedure of example 3 was repeated, except that: 1.0g of antimony trichloride was replaced with 0.5g of antimony trichloride and 0.5g of bismuth nitrate; catalyst H was obtained.
Catalyst H was packed in the fixed bed reactor and tested using molten salt at 352 ℃ and the results are shown in table 1.
[ example 9 ]
The procedure of example 1 was repeated, except that: 0.3g of indium acetate and 1.0g of bismuth nitrate were used in place of 1.3g of indium acetate; catalyst I was obtained.
Catalyst I was packed in the fixed bed reactor and tested using molten salt at 352 ℃ and 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 indium acetate was not added. After spraying and drying treatment, 397 of the catalyst precursor was obtained, the content of the active material being 16.9% based on the total mass of the catalyst.
Catalyst J was packed in the fixed bed reactor and tested using molten salt at 352℃and 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 an auxiliary compound. After spraying and drying treatment, 395 of the catalyst precursor was obtained, the content of active material being 16.5% based on the total mass of the catalyst.
Catalyst K was packed in the fixed bed reactor and tested using molten salt at 352℃and 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.
Catalyst L was packed in the fixed bed reactor and tested using molten salt at 352 ℃ and the results are shown in table 1.
[ Experimental example ]
And (3) filling the catalyst activated by the activation furnace into a 120mL bubbling molten salt circulating reactor, wherein the bottom of the reactor is supported by an inert carrier, the middle of the reactor is filled with 120mL of catalyst, and the upper part of the reactor is provided with the inert carrier with a certain height. When the molten salt is heated to the temperature required by the reaction, air is fed, benzene is simultaneously fed, and after the benzene concentration reaches the concentration of the required working condition, sampling analysis is started after the benzene concentration is stabilized for 1 hour, and the sampling evaluation results of each catalyst are shown in table 1.
The calculation method of each index is as follows:
benzene conversion (%) = (amount of benzene at reactor inlet per unit time-amount of benzene at reactor outlet per unit time)/amount of benzene at reactor inlet per unit time x 100%.
Maleic anhydride weight yield (%) =benzene conversion x maleic anhydride selectivity x 98/78 x 100%.
TABLE 1 results of 120mL single tube Activity evaluation
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art 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, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (25)

1. The catalyst for preparing maleic anhydride by benzene oxidation comprises a carrier and an active component loaded on the carrier, wherein the active component comprises a main catalyst and a cocatalyst, the main catalyst comprises vanadium element, molybdenum element, sodium element, phosphorus element and nickel element, and the cocatalyst comprises at least one of indium element and antimony element and boron element; 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 the molar ratio is respectively expressed by V 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, calculated as NiO molar amount, calculated as B 2 O 3 The molar amount is calculated by the molar amount of M element, and the M element is at least one selected from indium and antimony.
2. The maleic anhydride catalyst of claim 1, wherein the loading of the active component is from 10% to 20% based on the catalyst.
3. The maleic anhydride catalyst according to claim 2, wherein the loading of the active component is 14-18% based on the catalyst.
4. A catalyst for preparing maleic anhydride by benzene oxidation according to any one of claim 1 to 3,
the carrier is at least one selected from silicon carbide, alumina and silicon dioxide.
5. A method for preparing maleic anhydride catalyst by benzene oxidation according to one of claims 1 to 4, comprising the following steps:
step 1, adding a compound containing an active component into a reducer solution to obtain an active mother solution;
step 2, the active mother liquor is contacted with a carrier, and a catalyst precursor is obtained through drying;
and step 3, performing activation treatment on 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.
7. The production method according to claim 6, wherein the main catalyst compound comprises 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 an M-containing compound, wherein M is at least one of indium and antimony.
8. The method according to claim 7, wherein,
the vanadium compound is at least one selected from 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/or
The sodium compound is at least one selected from sodium dihydrogen phosphate and trisodium phosphate; and/or
The phosphorus compound is at least one selected from monoammonium phosphate, 85% -115% phosphoric acid and phosphorus pentoxide; and/or
The nickel compound is at least one selected from nickel nitrate, nickel sulfate, nickel chloride and nickel oxide.
9. The method according to claim 7, wherein,
the boron-containing compound is selected from at least one of boric acid, boron oxide and sodium borate; and/or
The M-containing compound is at least one selected from soluble salts containing M elements.
10. The method according to claim 9, wherein the M element is at least one of acetate, nitrate, and chloride containing the M element.
11. The method according to claim 7, wherein the vanadium compound and the molybdenum compound are: 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 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, calculated as NiO molar amount, calculated as B 2 O 3 Molar amount, based on the molar amount of M element.
12. The method according to claim 7, wherein,
in step 1, the reducing agent is selected from oxalic acid; and/or
In the step 2, before the contact, heating the carrier to 180-350 ℃; and/or
The active mother liquor is contacted with the carrier in a spray coating manner.
13. The method according to claim 12, wherein,
in the step 1, the molar ratio of the reducing agent to the vanadium compound is (1-3): 1; and/or
In step 2, the carrier is heated to 250-270 ℃ before said contacting; and/or
The spraying is carried out at 150-350 ℃.
14. The method according to claim 12, wherein,
in the step 1, the molar ratio of the reducing agent to the vanadium compound is (1.5-2.5): 1; and/or
In step 2, the carrier is heated to 250-270 ℃ before said contacting; and/or
The spraying speed is 0.05-1mL/min gcat.
15. The process according to claim 5, wherein the active component is supported in an amount of 10 to 30% by weight based on 100% by weight of the catalyst precursor.
16. The process of claim 15, wherein the active component is supported in an amount of 14% to 18% by weight based on 100% by weight of the catalyst precursor.
17. The method of any one of claims 5 to 16, 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.
18. The method of preparing according to claim 17, wherein the adhesive is selected from at least one of 704 glue, 705 glue, 706 glue, and 708 glue; and/or the pore expanding agent is at least one selected from ammonium carbonate, ammonium bicarbonate and ammonium chloride.
19. The method of claim 17, wherein the binder is present in an amount of 0.5 to 5% by weight of the total active mother liquor and the pore-expanding agent is present in an amount of 0.01 to 0.1% by weight of the total active mother liquor.
20. The method according to claim 17, wherein in step 3, the activation treatment is performed in an activation atmosphere selected from nitrogen and/or helium in a closed environment.
21. The method of claim 20, wherein the activation treatment is performed as follows:
3.1 Raising the temperature 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 220-250 ℃ at a heating rate of 60-120 ℃/h, and keeping for 5-30 minutes; 3.3 Raising the temperature to 300-350 ℃ at a heating rate of 50-100 ℃/h, and keeping for 10-60 minutes; 3.4 Raising the temperature to 420-480 ℃ at a heating rate of 40-90 ℃/h, and maintaining for 5-10 hours; 3.5 And cooling to room temperature at a rate of 40-80 ℃/h.
22. A maleic anhydride catalyst prepared by benzene oxidation obtained by the preparation method according to any one of claims 5 to 21.
23. Use of the maleic anhydride catalyst prepared by benzene oxidation according to any one of claims 1 to 4 or the maleic anhydride catalyst prepared by benzene oxidation obtained by the preparation method according to any one of claims 5 to 21 in preparing maleic anhydride by benzene oxidation.
24. The use according to claim 23, wherein the maleic anhydride is prepared by benzene oxidation as a molten salt circulation reaction, and the molten salt temperature is 340-360 ℃; and/or oxidizing the mixed gas of benzene and air through a fixed bed reactor filled with the catalyst to prepare maleic anhydride.
25. The use according to claim 24, wherein the benzene is at a working concentration of 40-55g/Nm 3 。
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US4118402A (en) * 1974-12-02 1978-10-03 Nippon Shokubai Kagaku Kogyo Co., Ltd. Preparation of maleic anhydride
CN1106714A (en) * 1994-07-05 1995-08-16 化学工业部北京化工研究院 Maleic anhydride catalyst with heavy rare earth oxide and its application
CN102196859A (en) * 2008-08-29 2011-09-21 约瑟夫·布赖梅尔 Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and/or carboxylic acid anhydrides, in particular phthalic acid anhydride, and method for producing said type of catalyst
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
CN113842934A (en) * 2020-06-28 2021-12-28 中国石油化工股份有限公司 Oxidation catalyst and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN1106714A (en) * 1994-07-05 1995-08-16 化学工业部北京化工研究院 Maleic anhydride catalyst with heavy rare earth oxide and its application
CN102196859A (en) * 2008-08-29 2011-09-21 约瑟夫·布赖梅尔 Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and/or carboxylic acid anhydrides, in particular phthalic acid anhydride, and method for producing said type of catalyst
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
CN113842934A (en) * 2020-06-28 2021-12-28 中国石油化工股份有限公司 Oxidation catalyst and preparation method and application thereof

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