CN117138813A - Vanadium-molybdenum maleic anhydride catalyst, preparation method and application - Google Patents

Vanadium-molybdenum maleic anhydride catalyst, preparation method and application Download PDF

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CN117138813A
CN117138813A CN202210569681.8A CN202210569681A CN117138813A CN 117138813 A CN117138813 A CN 117138813A CN 202210569681 A CN202210569681 A CN 202210569681A CN 117138813 A CN117138813 A CN 117138813A
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oxide
active component
precursor
catalyst
calculated
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张东顺
师慧敏
张作峰
冯晔
韩鑫宇
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Priority to CN202210569681.8A priority Critical patent/CN117138813A/en
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of maleic anhydride preparation by benzene oxidation, and discloses a vanadium-molybdenum maleic anhydride catalyst, a preparation method and application thereof, wherein the catalyst comprises a carrier and an active component loaded on the carrier, and the active component comprises a first active component, a second active component and a third active component; the first active component includes oxides of vanadium, molybdenum, sodium, phosphorus, and nickel; the second active component comprises at least one of an oxide of germanium, an oxide of selenium, and an oxide of strontium; the third active component includes at least one of an oxide of titanium, an oxide of zirconium, an oxide of iridium, an oxide of rhodium, an oxide of iron, and an oxide of niobium. The catalyst of the invention can improve the selectivity and the yield of maleic anhydride.

Description

Vanadium-molybdenum maleic anhydride catalyst, preparation method and application
Technical Field
The invention relates to the technical field of maleic anhydride preparation by benzene oxidation, in particular to a vanadium-molybdenum maleic anhydride catalyst, a preparation method and application thereof.
Background
Maleic anhydride (maleic anhydride) is a very important organic chemical raw material, and is the second largest organic anhydride next to phthalic anhydride. As a chemical intermediate. Maleic anhydride has very wide application, can be used for producing Unsaturated Polyester Resin (UPR), 1, 4-succinic acid, 1, 4-butanediol, tetrahydrofuran, gamma-butyrolactone, malic acid and other products, and can also be used for producing medicines, pesticides and food additives. Unsaturated Polyester Resins (UPR) are the largest consumer products downstream of maleic anhydride and can be used in amounts of more than 60% of the total maleic anhydride consumed.
The production process of maleic anhydride can be classified into benzene method and n-butane method according to the source and kind of raw materials. With the continuous perfection and development of the n-butane technology, the production capacity of the n-butane oxidation method device which is more environment-friendly is continuously enlarged, and the development is rapid. However, the process of maleic anhydride preparation by n-butane is more complex than the benzene method, and particularly, the process involves a solvent absorption process and is relatively complex to operate, so that the process using benzene as a raw material still has more markets. In addition, in recent years, the price of benzene also continuously fluctuates, the price is at a lower level, the price of n-butane is not changed greatly, and the benzene method still has certain comprehensive advantages by combining the operation cost of the benzene method and the maleic anhydride device of the butane method.
In the areas with relatively abundant coal resources and relatively deficient petroleum resources, such as western areas of Shanxi province, the coal chemical industry resources are abundant, so that a large amount of coking benzene is generated, and the maleic anhydride device adopting the coking benzene as the raw material still has larger productivity. At present, in order to improve the economic benefit, the manufacturers reduce the production cost as much as possible, optimize the process as much as possible, reduce the benzene consumption, reduce byproducts, improve the selectivity of maleic anhydride and further improve the economic benefit.
At present, a plurality of patent applications for preparing maleic anhydride catalysts by benzene oxidation exist, some patent applications relate to preparation of carriers designed by the patent applications, some patent applications relate to optimization of process technology, and other patent applications relate to screening of metal auxiliary agents and optimization formulas, for example, a preparation method for preparing maleic anhydride catalysts by benzene oxidation is provided in CN103816931A, VIII family copper elements are adopted as auxiliary agents, hydrochloric acid is adopted as a reducing agent, mixed solution is sprayed on inert talcum porcelain carriers, and then activation is carried out at the temperature of 350-450 ℃ under the atmosphere of inert gas, so that an active catalyst is obtained. The patent application uses hydrochloric acid, which is a very volatile and corrosive acid, which not only causes serious corrosion of equipment and increases equipment investment cost, but also damages the health of workers and generates a great amount of waste acid water and other environmental problems. CN105536837a discloses a catalyst for preparing maleic anhydride by benzene oxidation, which is prepared by using rare earth metal oxide as main auxiliary agent, such as one or more of lanthanum, cerium, terbium and europium, and silicon carbide as carrier, and using impregnation method or spray method. CN102850306 proposes a catalyst for preparing maleic anhydride by benzene oxidation with a double-stage bed, the technology of the double-stage bed is adopted, the upper-stage catalyst adopts the combination of an auxiliary group element and a lanthanide, the lower stage contains the auxiliary group element, and the phosphorus-vanadium ratio of the upper-stage bed layer and the lower-stage bed layer is regulated. The process uses a double-stage bed process, and the catalyst is filled with complex catalyst and benzene load is higher than the operation level of the common benzene maleic anhydride manufacturer in China at present although the yield is higher.
Disclosure of Invention
Benzene oxidation maleic anhydride preparation reaction belongs to gas-solid phase reaction, gaseous benzene molecules can diffuse to the surface of a catalyst, adsorption, bond breaking, bond formation, desorption and other reactions can occur on the surface of the catalyst, wherein the adsorption and desorption of benzene and maleic anhydride play a very important role in the reaction process, the benzene adsorption time is short, the desorption is fast, and the benzene conversion rate is reduced; maleic anhydride has long desorption time and is easy to deeply oxidize to generate carbon dioxide and carbon monoxide. In the catalyst for benzene oxidation reaction, the main crystal form is V 2 MoO 8 The inventors found that the valence and crystal structure of the vanadium as a central atom can be changed by simultaneously introducing the second active component and the third active component as an auxiliary agent into a catalyst using the oxide of vanadium, the oxide of molybdenum, the oxide of sodium, the oxide of phosphorus and the oxide of nickel as the first active component, thereby improving the performance of the catalyst.
Thus, in order to achieve the above object, the first aspect of the present invention provides a vanadium-molybdenum-based maleic anhydride catalyst comprising a support and an active component supported on the support, the active component comprising a first active component, a second active component and a third active component;
the first active component includes oxides of vanadium, molybdenum, sodium, phosphorus, and nickel;
the second active component comprises at least one of an oxide of germanium, an oxide of selenium, and an oxide of strontium;
the third active component includes at least one of an oxide of titanium, an oxide of zirconium, an oxide of iridium, an oxide of rhodium, an oxide of iron, and an oxide of niobium.
The second aspect of the invention provides a method for preparing vanadium-molybdenum maleic anhydride catalyst, which comprises loading active component precursor on a carrier to obtain catalyst precursor, and activating; the active component precursor comprises a first active component precursor, a second active component precursor and a third active component precursor;
the first active component precursor comprises an oxide precursor of vanadium, an oxide precursor of molybdenum, an oxide precursor of sodium, an oxide precursor of phosphorus and an oxide precursor of nickel;
the second active component precursor comprises at least one of an oxide precursor of selenium, an oxide precursor of germanium and an oxide precursor of strontium;
the third reactive species precursor comprises at least one of an oxide precursor of titanium, an oxide precursor of zirconium, an oxide precursor of iridium, an oxide precursor of rhodium, an oxide precursor of iron, and an oxide precursor of niobium.
In a third aspect, the present invention provides a catalyst prepared by the method described above.
In a fourth aspect, the invention provides the use of a catalyst as described above or a catalyst prepared by a method as described above in the preparation of maleic anhydride by oxidation of benzene.
In a fifth aspect, the present invention provides a method for preparing maleic anhydride by benzene oxidation, comprising: contacting benzene with oxygen in the presence of the catalyst;
alternatively, the method comprises: the catalyst is prepared as described above and benzene is contacted with oxygen in the presence of the catalyst.
The second active component and the third active component are introduced into the catalyst of vanadium oxide, molybdenum oxide, sodium oxide, phosphorus oxide and nickel oxide, so that the valence state of the central atom vanadium can be changed, and the performance of the catalyst is improved. The catalyst of the invention can obtain higher benzene conversion rate, maleic anhydride selectivity and weight yield at lower reaction temperature. Meanwhile, under the condition of single use (namely, the catalyst is not used in combination with other catalysts to carry out sectional filling), the catalyst can also obtain higher benzene conversion rate, maleic anhydride selectivity and weight yield.
In a preferred embodiment, the present invention further provides for improved maleic anhydride selectivity and yield by using polyethylene glycol and a hard ester in the preparation of the catalyst.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. 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.
The invention provides a vanadium-molybdenum maleic anhydride catalyst, which comprises a carrier and an active component supported on the carrier, wherein the active component comprises a first active component, a second active component and a third active component;
the first active component includes oxides of vanadium, molybdenum, sodium, phosphorus, and nickel;
the second active component comprises at least one of an oxide of germanium, an oxide of selenium, and an oxide of strontium;
the third active component includes at least one of an oxide of titanium, an oxide of zirconium, an oxide of iridium, an oxide of rhodium, an oxide of iron, and an oxide of niobium.
According to the present invention, preferably, the carrier is silicon carbide. The carrier can be in any one of a sphere, a cylinder, a ring, a clover and a clover.
According to the present invention, preferably, the combination of the second active component and the third active component is selected from at least one of a combination of strontium oxide and niobium oxide, a combination of germanium oxide and iridium oxide, a combination of selenium oxide and zirconium oxide, and a combination of strontium oxide and zirconium oxide. When the combination of the second active component and the third active component is selected from the group consisting of oxides of strontium and niobium, it is understood that the second active component is selected from the group consisting of oxides of strontium and the third active component is selected from the group consisting of oxides of niobium.
According to the invention, the active component is preferably present in an amount of from 10 to 20% by weight and the support in an amount of from 80 to 90% by weight, based on the total weight of the catalyst.
According to the present invention, preferably, the catalyst does not contain a lanthanide metal element.
According to the present invention, it is preferable that the molar ratio of the first active component in terms of non-oxygen element, the second active component in terms of non-oxygen element, and the third active component in terms of non-oxygen element is 1:0.0001-0.1:0.0001-0.1.
According to the invention, preferably in V 2 O 5 Calculated as oxide of vanadium in MoO 3 Calculated as oxides of molybdenum, expressed as Na 2 Oxide of sodium calculated as O, in P 2 O 5 The molar ratio of phosphorus oxide to nickel oxide calculated as NiO, the second active component calculated as oxide, the third active component calculated as oxide is 1:0.2-0.9:0.001-0.2:0.005-0.25:0.0001-0.05:0.0001-0.06:0.0001-0.08, preferably 1:0.5-0.8:0.01-0.1:0.01-0.1:0.01-0.02:0.0005-0.05:0.005-0.05, more preferably 1:0.55-0.7:0.04-0.08:0.01-0.05:0.015-0.02:0.0005-0.05:0.005-0.05.
The second aspect of the invention provides a method for preparing vanadium-molybdenum maleic anhydride catalyst, which comprises loading active component precursor on a carrier to obtain catalyst precursor, and activating; the active component precursor comprises a first active component precursor, a second active component precursor and a third active component precursor;
the first active component precursor comprises an oxide precursor of vanadium, an oxide precursor of molybdenum, an oxide precursor of sodium, an oxide precursor of phosphorus and an oxide precursor of nickel;
the second active component precursor comprises at least one of an oxide precursor of selenium, an oxide precursor of germanium and an oxide precursor of strontium;
the third reactive species precursor comprises at least one of an oxide precursor of titanium, an oxide precursor of zirconium, an oxide precursor of iridium, an oxide precursor of rhodium, an oxide precursor of iron, and an oxide precursor of niobium.
According to the present invention, preferably, the carrier is silicon carbide. The carrier can be in any one of a sphere, a cylinder, a ring, a clover and a clover.
According to the present invention, preferably, the combination of the second active component precursor and the third active component precursor is selected from at least one of a combination of an oxide precursor of strontium and an oxide precursor of niobium, a combination of an oxide precursor of germanium and an oxide precursor of iridium, a combination of an oxide precursor of selenium and an oxide precursor of zirconium, and a combination of an oxide precursor of strontium and an oxide precursor of zirconium.
According to the present invention, it is preferable that the active component precursor and the carrier are used in such an amount that the catalyst is prepared such that the active component is contained in an amount of 10 to 20% by weight and the carrier is contained in an amount of 80 to 90% by weight, based on the total weight of the catalyst.
According to the present invention, preferably, the first active component precursor, the second active component precursor and the third active component precursor are used in such an amount that the molar ratio of the first active component in terms of non-oxygen element, the second active component in terms of non-oxygen element and the third active component in terms of non-oxygen element in the catalyst is 1:0.0001-0.1:0.0001-0.1.
According to the invention, the active component precursor is preferably used in such an amount that the catalyst obtained is in V 2 O 5 Calculated as oxide of vanadium in MoO 3 Calculated as oxides of molybdenum, expressed as Na 2 Oxide of sodium calculated as O, in P 2 O 5 The molar ratio of phosphorus oxide to nickel oxide calculated as NiO, the second active component calculated as oxide, the third active component calculated as oxide is 1:0.2-0.9:0.001-0.2:0.005-0.25:0.0001-0.05:0.0001-0.06:0.0001-0.08, preferably 1:0.5-0.8:0.01-0.1:0.01-0.1:0.01-0.02:0.0005-0.05:0.005-0.05, more preferably 1:0.55-0.7:0.04-0.08:0.01-0.05:0.015-0.02:0.0005-0.05:0.005-0.05.
According to the present invention, preferably, the load includes:
(1) Mixing a solvent, an active component precursor, polyethylene glycol and stearic acid to obtain a mixture containing the active component precursor;
(2) Coating the mixture obtained in the step (1) on a carrier to obtain a catalyst precursor.
According to the present invention, the polyethylene glycol is preferably used in an amount of 0.1 to 5g, more preferably 0.4 to 2g, per 100g of the solvent.
According to the present invention, preferably, the polyethylene glycol has a weight average molecular weight of 1500 to 2000g/mol. For example, PEG-1500 (polyethylene glycol having a weight average molecular weight of 1500), PEG-2000 (polyethylene glycol having a weight average molecular weight of 2000).
According to the present invention, it is preferable that the stearic acid is used in an amount of 2 to 10g per 100g of the solvent.
According to the present invention, preferably, the stearic acid has a particle size of 10 to 50 microns.
According to the invention, the oxide precursor of vanadium is any substance capable of providing elemental vanadium, preferably the oxide precursor of vanadium is ammonium metavanadate.
According to the present invention, the molybdenum oxide precursor is any substance capable of providing elemental molybdenum, preferably, the molybdenum oxide precursor is selected from at least one of ammonium molybdate, molybdenum trioxide, and calcium molybdate, more preferably, ammonium molybdate.
According to the present invention, the sodium oxide precursor is any substance capable of providing elemental sodium, preferably, the sodium oxide precursor is selected from at least one of sodium dihydrogen phosphate and trisodium phosphate, more preferably trisodium phosphate.
According to the present invention, the oxide precursor of phosphorus is any substance capable of providing elemental phosphorus, preferably, the oxide precursor of phosphorus is selected from at least one of monoammonium phosphate, 85% -115% phosphoric acid, phosphorus pentoxide, sodium dihydrogen phosphate, and trisodium phosphate, more preferably, monoammonium phosphate and or trisodium phosphate.
According to the present invention, the oxide precursor of nickel is any substance capable of providing elemental nickel, preferably, the oxide precursor of nickel is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, and nickel oxide, more preferably, nickel nitrate.
According to the present invention, preferably, the second active component precursor is any substance capable of providing an element of the second active component.
According to the present invention, preferably, the third active component precursor is any substance capable of providing a third active component element.
According to the present invention, preferably, step (2) further comprises subjecting the mixture to ultrasonic treatment prior to coating, the conditions of the ultrasonic treatment comprising: the ultrasonic frequency is 30-40KHz, and the ultrasonic time is 1-20min.
According to the present invention, there is no limitation in the manner of coating, and conventional technical means in the prior art may be employed, and preferably, the manner of coating is: the carrier is coated with the mother liquor containing the active ingredient precursor and then dried. Wherein, the drying conditions may include: the temperature is 100-150 ℃ and the time is 2-8h.
The apparatus for the coating according to the present invention is not particularly limited as long as the active ingredient can be supported on a carrier. Preferably, the coating is performed in a rotatable and heatable stainless steel drum, a thermowell is arranged in the stainless steel drum for heating the carrier, the temperature of the thermowell is controllable and provided with a temperature display, the change of the temperature of the carrier can be detected in real time in the coating process, and the active component precursor is sprayed onto the carrier through a nozzle to finish the coating. More preferably, the stainless steel drum is rotated at 10-40rpm/min during the coating process, and the spray coating temperature is 250-300 c while maintaining the carrier temperature at 260-270 c when the carrier is heated to 250-270 c.
According to the present invention, preferably, the activated temperature control program includes: raising the temperature to 150-170 ℃ at a heating rate of 70-150 ℃/h, maintaining for 5-30min, raising the temperature to 250-280 ℃ at a heating rate of 60-120 ℃/h, maintaining for 5-30min, raising the temperature to 350-380 ℃ at a heating rate of 50-100 ℃/h, maintaining for 10-60min, raising the temperature to 420-480 ℃ at a heating rate of 40-90 ℃/h, maintaining for 5-10h, and then lowering the temperature to 15-40 ℃ at a heating rate of 40-80 ℃/h.
According to the invention, preferably, the activation is carried out in a closed container. 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.
According to the present invention, preferably, the activation may be performed in a closed environment, and the atmosphere for activation may be an atmosphere of nitrogen and/or helium.
In a third aspect, the present invention provides a catalyst prepared by the method described above.
In a fourth aspect, the invention provides the use of a catalyst as described above or a catalyst prepared by a method as described above in the preparation of maleic anhydride by oxidation of benzene.
In a fifth aspect, the present invention provides a method for preparing maleic anhydride by benzene oxidation, comprising: contacting benzene with oxygen in the presence of the catalyst;
alternatively, the method comprises: the catalyst is prepared as described above and benzene is contacted with oxygen in the presence of the catalyst.
According to the present invention, preferably, the oxygen is contacted with benzene in the form of air, and in order to prevent the risk of the benzene concentration being excessively high, more preferably, the benzene concentration in the mixture of benzene and air is 40 to 55g/Nm 3 . Benzene concentration refers to the mass number of benzene contained in a unit volume of air, and the higher the value in grams, the higher the benzene content in the air.
According to the invention, preferably, the volume space velocity of the mixture of benzene and air is 1500-3000h -1 More preferably 2000-2500h -1 。
The benzene and oxygen may be contacted under normal pressure, pressurized, or under negative pressure, and preferably, the benzene and oxygen are contacted under normal pressure.
According to the invention, the process of the invention uses a fixed bed reactor, and a molten salt bath can be used for heating and removing the heat of reaction in the process of preparing maleic anhydride by benzene oxidation, and the temperature of the molten salt is preferably 340-360 ℃. 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, the height of the corresponding bed is the hot spot position of the catalyst, and the hot spot temperature is measured by using a thermocouple through the broaching of the bed.
The present invention will be described in detail by examples. In the following examples of the present invention,
the room temperature is about "25 ℃.
Example 1
Step A: 98g of oxalic acid is dissolved in 490mL of water at room temperature, 69.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved to form a uniform and stable solution, and 2.45g of PEG-1500 is added at the moment; dissolving ammonium molybdate in 50mL of water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; trisodium phosphate, nickel nitrate, strontium nitrate and ammonium niobium oxalate are sequentially added under stirring, then 3.0g of stearic acid (the particle size is 10-20 microns) is added, ultrasonic is carried out for 5min under ultrasonic wave, the frequency is selected to be 35KHz, and the mixture containing the active component precursors is prepared after mixing.
And (B) step (B): 330g of carrier (silicon carbide) 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. And regulating the rotating speed of the rotating drum to be 10-20 revolutions per minute, spraying the mixture containing the active component precursor onto the carrier through a nozzle when the temperature of the carrier is heated to 250 ℃, wherein the spraying speed is 0.08mL/min gcat, the spraying temperature is 250-270 ℃, and drying the mixture at 120 ℃ for 4 hours after the spraying is finished, so as to obtain the catalyst precursor. The weight of the catalyst precursor was 404g.
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 at 350℃and then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to prepare a catalyst.
The catalyst thus obtained was weighed, and the content of the active component was 18.0% by weight and the content of the carrier was 82.0% by weight based on the total amount of the catalyst.
The molar ratio of vanadium oxide, molybdenum oxide, sodium oxide, phosphorus oxide, nickel oxide, strontium oxide and niobium oxide in the active component of the catalyst was determined by XRF elemental analysis to be 1:0.61:0.06:0.02:0.017:0.008:0.01, wherein the oxide of vanadium is represented by V 2 O 5 Calculated as MoO for molybdenum oxide 3 Calculated as Na and oxide of sodium 2 O is calculated, oxide of phosphorus is calculated as P 2 O 5 Calculated as NiO, calculated as strontium oxide, calculated as SrO, calculated as Nb 2 O 5 And (5) counting.
Example 2
The catalyst preparation was carried out as in example 1, except that PEG-1500 was added in an amount of 9.8g.
Example 3
The catalyst preparation was carried out as in example 1, except that the amount of PEG-1500 added was 9.8g, while varying the amount of strontium nitrate added.
The catalyst thus obtained was weighed, and the content of the active component was 17.9% by weight and the content of the carrier was 82.1% by weight based on the total amount of the catalyst.
The molar ratio of vanadium oxide, molybdenum oxide, sodium oxide, phosphorus oxide, nickel oxide, strontium oxide and niobium oxide in the active component of the catalyst was determined by XRF elemental analysis to be 1:0.61:0.06:0.02:0.017:0.003:0.01, wherein the oxide of vanadium is represented by V 2 O 5 Calculated as MoO for molybdenum oxide 3 Calculated as Na and oxide of sodium 2 O is calculated, oxide of phosphorus is calculated as P 2 O 5 Calculated as NiO, calculated as strontium oxide, calculated as SrO, calculated as Nb 2 O 5 And (5) counting.
Example 4
The catalyst preparation was carried out as in example 1, except that "strontium nitrate and ammonium niobium oxalate" were replaced with "germanium tetrachloride and chloroiridic acid", and the amounts of germanium tetrachloride and chloroiridic acid were different from those of strontium nitrate and ammonium niobium oxalate.
The catalyst thus obtained was weighed, and the content of the active component was 17.8% by weight and the content of the carrier was 82.2% by weight based on the total amount of the catalyst.
The molar ratio of vanadium oxide, molybdenum oxide, sodium oxide, phosphorus oxide, nickel oxide, germanium oxide and iridium oxide in the active component of the catalyst is 1:0.61:0.06:0.02:0.017:0.0009:0.03, wherein,the oxide of vanadium is expressed as V 2 O 5 Calculated as MoO for molybdenum oxide 3 Calculated as Na and oxide of sodium 2 O is calculated, oxide of phosphorus is calculated as P 2 O 5 Calculated as NiO for nickel oxide and GeO for germanium oxide 2 Iridium oxide as IrO 2 And (5) counting.
Example 5
The catalyst preparation was carried out as in example 1, except that "strontium nitrate and ammonium niobium oxalate" were replaced with "selenate and zirconium nitrate", and that the amounts of selenate and zirconium nitrate were different from those of strontium nitrate and ammonium niobium oxalate.
The catalyst thus obtained was weighed, and the content of the active component was 17.8% by weight and the content of the carrier was 82.2% by weight based on the total amount of the catalyst.
The molar ratio of vanadium oxide, molybdenum oxide, sodium oxide, phosphorus oxide, nickel oxide, selenium oxide and zirconium oxide in the active component of the catalyst was 1:0.61:0.06:0.02:0.017:0.001:0.03, wherein the oxide of vanadium is represented by V 2 O 5 Calculated as MoO for molybdenum oxide 3 Calculated as Na and oxide of sodium 2 O is calculated, oxide of phosphorus is calculated as P 2 O 5 The oxide of nickel is calculated as NiO, and the oxide of selenium is calculated as SeO 2 Zirconium oxide is expressed as ZrO 2 And (5) counting.
Example 6
The catalyst preparation was carried out as in example 1, except that "ammonium niobium oxalate" was replaced with "zirconium nitrate" and the amount of zirconium nitrate was different from that of ammonium niobium oxalate.
The catalyst thus obtained was weighed, and the content of the active component was 17.9% by weight and the content of the carrier was 82.1% by weight based on the total amount of the catalyst.
The molar ratio of vanadium oxide, molybdenum oxide, sodium oxide, phosphorus oxide, nickel oxide, strontium oxide and zirconium oxide in the active component of the catalyst was determined by XRF elemental analysis to be 1:0.61:0.06:0.02:0.017:0.008:0.017, wherein the oxygen of vanadiumThe chemical compound is V 2 O 5 Calculated as MoO for molybdenum oxide 3 Calculated as Na and oxide of sodium 2 O is calculated, oxide of phosphorus is calculated as P 2 O 5 The oxide of nickel is calculated as NiO, the oxide of strontium is calculated as SrO, and the oxide of zirconium is calculated as ZrO 2 And (5) counting.
Example 7
The catalyst preparation was carried out as in example 1, except that PEG-1500 was replaced with PEG-2000 of equal mass, while varying the amount of ammonium niobium oxalate added.
The catalyst thus obtained was weighed, and the content of the active component was 17.8% by weight and the content of the carrier was 82.1% by weight based on the total amount of the catalyst.
The molar ratio of vanadium oxide, molybdenum oxide, sodium oxide, phosphorus oxide, nickel oxide, strontium oxide and niobium oxide in the active component of the catalyst was determined by XRF elemental analysis to be 1:0.61:0.06:0.02:0.017:0.008:0.009 in which the oxide of vanadium is present as V 2 O 5 Calculated as MoO for molybdenum oxide 3 Calculated as Na and oxide of sodium 2 O is calculated, oxide of phosphorus is calculated as P 2 O 5 Calculated as NiO, calculated as strontium oxide, calculated as SrO, calculated as Nb 2 O 5 And (5) counting.
Example 8
The catalyst preparation was carried out as in example 7, except that PEG-2000 was added in an amount of 6.1g.
Example 9
The catalyst preparation was carried out as in example 7, except that PEG-2000 was added in an amount of 9.8g.
Example 10
The catalyst preparation was carried out as in example 1, except that PEG-1500 was not added.
Example 11
The catalyst preparation was carried out as in example 1, except that no stearic acid was added.
Example 12
The catalyst preparation was carried out as in example 1, except that stearic acid was added in an amount of 8g.
Example 13
The catalyst preparation was carried out as in example 1, except that the particle size of stearic acid was 30-40 microns.
Example 14
The catalyst preparation was performed as in example 1, except that PEG-1500 was replaced with PEG-6000 of equal mass.
Example 15
The catalyst preparation was carried out as in example 1, except that stearic acid was replaced with equal mass of methyl stearate.
Comparative example 1
The catalyst preparation was carried out as in example 1, except that ammonium niobium oxalate was not added.
Comparative example 2
The catalyst preparation was carried out as in example 1, except that strontium nitrate was not added.
Comparative example 3
The catalyst preparation was carried out as in example 1, except that strontium nitrate and PEG-1500 were not added.
Comparative example 4
The catalyst preparation was carried out as in example 1, except that ammonium niobium oxalate was replaced with equimolar strontium nitrate.
Comparative example 5
The catalyst preparation was carried out as in example 1, except that strontium nitrate was replaced with equimolar ammonium niobium oxalate.
Comparative example 6
The catalyst preparation was carried out as in example 1, except that strontium nitrate was replaced with equimolar chromium nitrate.
Test case
The catalyst prepared in the above examples and comparative examples is filled in a 120ml bubbling molten salt circulating reactor, the bottom of the reactor is supported by an inert carrier, 120ml of catalyst is filled in the middle, and the upper part is provided with an inert with a certain heightA sexual carrier. When the molten salt is heated to the temperature required by the reaction, air is fed, benzene is simultaneously fed, and the volume space velocity of the mixed gas of the benzene and the air is 2200h -1 . When the benzene concentration reached the desired working condition concentration (benzene concentration 45g/Nm 3 ) After stabilization for 1 hour, sampling analysis was started, and the results of sampling evaluation 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 selectivity (%) = amount of benzene converted to maleic anhydride per unit time/(amount of benzene at reactor inlet per unit time-amount of benzene at reactor outlet per unit time) ×100%;
maleic anhydride weight yield (%) =benzene conversion x maleic anhydride selectivity x 98/78 x 100%.
TABLE 1
As can be seen from the results of Table 1, the conversion of benzene, the selectivity for maleic anhydride and the weight yield can be improved by using the catalyst of the present invention, and comparing the examples and comparative examples in Table 1, it can be seen that the weight yield of maleic anhydride can be greatly improved when the prepared catalyst contains the first active component, the second active component and the third active component at the same time; the addition of stearic acid and polyethylene glycol during the catalyst preparation process is beneficial to further improving the performance of the catalyst. The catalyst of the invention can obtain higher benzene conversion rate, maleic anhydride selectivity and weight yield at lower reaction temperature.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (11)

1. A vanadium-molybdenum maleic anhydride catalyst, characterized in that the catalyst comprises a carrier and an active component supported on the carrier, wherein the active component comprises a first active component, a second active component and a third active component;
the first active component includes oxides of vanadium, molybdenum, sodium, phosphorus, and nickel;
the second active component comprises at least one of an oxide of germanium, an oxide of selenium, and an oxide of strontium;
the third active component includes at least one of an oxide of titanium, an oxide of zirconium, an oxide of iridium, an oxide of rhodium, an oxide of iron, and an oxide of niobium.
2. The catalyst of claim 1, wherein the combination of the second active component and the third active component is selected from at least one of a combination of strontium oxide and niobium oxide, a combination of germanium oxide and iridium oxide, a combination of selenium oxide and zirconium oxide, and a combination of strontium oxide and zirconium oxide;
and/or, the content of the active component is 10-20 wt% based on the total weight of the catalyst, and the content of the carrier is 80-90 wt%;
and/or the catalyst does not contain lanthanide metal elements.
3. The catalyst according to claim 2, wherein the molar ratio of the first active component in terms of non-oxygen element, the second active component in terms of non-oxygen element and the third active component in terms of non-oxygen element is 1:0.0001-0.1:0.0001-0.1;
and/or in V 2 O 5 Calculated as oxide of vanadium in MoO 3 Calculated as oxides of molybdenum, expressed as Na 2 Oxide of sodium calculated as O, in P 2 O 5 Phosphorus oxide and nickel oxide as NiO,The molar ratio of the second active component calculated as oxide to the third active component calculated as oxide is 1:0.2-0.9:0.001-0.2:0.005-0.25:0.0001-0.05:0.0001-0.06:0.0001-0.08.
4. A method for preparing vanadium-molybdenum maleic anhydride catalyst is characterized in that the method comprises the steps of loading active component precursors on a carrier to obtain catalyst precursors, and then activating the catalyst precursors; the active component precursor comprises a first active component precursor, a second active component precursor and a third active component precursor;
the first active component precursor comprises an oxide precursor of vanadium, an oxide precursor of molybdenum, an oxide precursor of sodium, an oxide precursor of phosphorus and an oxide precursor of nickel;
the second active component precursor comprises at least one of an oxide precursor of selenium, an oxide precursor of germanium and an oxide precursor of strontium;
the third reactive species precursor comprises at least one of an oxide precursor of titanium, an oxide precursor of zirconium, an oxide precursor of iridium, an oxide precursor of rhodium, an oxide precursor of iron, and an oxide precursor of niobium.
5. The method of claim 4, wherein the combination of the second active component precursor and the third active component precursor is selected from at least one of a combination of an oxide precursor of strontium and an oxide precursor of niobium, a combination of an oxide precursor of germanium and an oxide precursor of iridium, a combination of an oxide precursor of selenium and an oxide precursor of zirconium, and a combination of an oxide precursor of strontium and an oxide precursor of zirconium;
and/or the active component precursors and the carriers are used in an amount such that the content of the active component is 10-20 wt% and the content of the carrier is 80-90 wt% based on the total weight of the catalyst in the prepared catalyst.
6. The method of claim 5, wherein the first, second, and third reactive component precursors are used in amounts such that the molar ratio of the first reactive component to the second reactive component to the third reactive component to the non-oxygen element in the catalyst is 1:0.0001-0.1:0.0001-0.1;
and/or the amount of the active component precursor is such that V in the catalyst obtained 2 O 5 Calculated as oxide of vanadium in MoO 3 Calculated as oxides of molybdenum, expressed as Na 2 Oxide of sodium calculated as O, in P 2 O 5 The molar ratio of phosphorus oxide to nickel oxide calculated as NiO, the second active component calculated as oxide, the third active component calculated as oxide is 1:0.2-0.9:0.001-0.2:0.005-0.25:0.0001-0.05:0.0001-0.06:0.0001-0.08.
7. The method of claim 5, wherein the load comprises:
(1) Mixing a solvent, an active component precursor, polyethylene glycol and stearic acid to obtain a mixture containing the active component precursor;
(2) Coating the mixture obtained in the step (1) on a carrier to obtain a catalyst precursor.
8. The method according to claim 7, wherein the polyethylene glycol is used in an amount of 0.1 to 5g per 100g of solvent;
and/or, the weight average molecular weight of the polyethylene glycol is 1500-2000g/mol;
and/or, the stearic acid is used in an amount of 2 to 10g per 100g of solvent;
and/or the stearic acid has a particle size of 10-50 microns.
9. A catalyst prepared by the method of any one of claims 4-8.
10. Use of the catalyst of any one of claims 1-3 or the catalyst prepared by the method of any one of claims 4-8 in the preparation of maleic anhydride by oxidation of benzene.
11. A method for preparing maleic anhydride by benzene oxidation, which is characterized by comprising the following steps: contacting benzene with oxygen in the presence of the catalyst of any one of claims 1-3 and 9;
alternatively, the method comprises: a catalyst prepared according to the method of any one of claims 4 to 8, and benzene is contacted with oxygen in the presence of the catalyst.
CN202210569681.8A 2022-05-24 2022-05-24 Vanadium-molybdenum maleic anhydride catalyst, preparation method and application Pending CN117138813A (en)

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