CN107866245B - Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof - Google Patents

Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof Download PDF

Info

Publication number
CN107866245B
CN107866245B CN201610849412.1A CN201610849412A CN107866245B CN 107866245 B CN107866245 B CN 107866245B CN 201610849412 A CN201610849412 A CN 201610849412A CN 107866245 B CN107866245 B CN 107866245B
Authority
CN
China
Prior art keywords
catalyst
maleic anhydride
butane
preparing
pore
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610849412.1A
Other languages
Chinese (zh)
Other versions
CN107866245A (en
Inventor
赵欣
顾龙勤
曾炜
徐俊峰
陈亮
王丹柳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201610849412.1A priority Critical patent/CN107866245B/en
Publication of CN107866245A publication Critical patent/CN107866245A/en
Application granted granted Critical
Publication of CN107866245B publication Critical patent/CN107866245B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198Vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34Heterocyclic 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
    • C07D307/56Heterocyclic 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
    • C07D307/60Two oxygen atoms, e.g. succinic anhydride

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

The invention relates to a catalyst for preparing maleic anhydride by oxidizing n-butane. Mainly solves the problem of lower catalytic activity in the prior art. The main body of the invention comprises three elements of vanadium, phosphorus and oxygen, and a certain amount of metal auxiliary agent is added; the catalyst comprises the following components in percentage by weight based on the total weight of the catalyst: 26-35% of vanadium element, 14-20% of phosphorus element and 30-50% of oxygen element; the metal auxiliary agent is 0.02-7% of catalyst, and the catalyst is subjected to constant temperature and humidity treatment, multiple times of doping pore-forming agent and secondary forming treatment, so that the catalytic performance of the catalyst is improved, the strength of the catalyst is improved, and the catalyst can be applied to the field of preparing maleic anhydride by oxidizing n-butane.

Description

Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof
Technical Field
The invention relates to a catalyst for a reaction of preparing maleic anhydride by oxidizing n-butane and a preparation method thereof.
Background
Maleic anhydride, called maleic anhydride for short, is a common important organic chemical raw material, and is the third largest anhydride product with the world consumption second to that of phthalic anhydride and acetic anhydride. Maleic anhydride is widely applied to the industries of petrochemical industry, food chemical industry, medicine, building materials and the like, and is mainly used for synthesizing a series of important organic chemicals and fine chemicals such as unsaturated polyester resin, lubricating oil additive, food additive, 1, 4-Butanediol (BDO), gamma-butyrolactone (GBL), Tetrahydrofuran (THF) and the like.
The early production of maleic anhydride was prepared by the selective oxidation of benzene, but the proportion of benzene process in maleic anhydride production is decreasing due to the hazard of benzene to human body and environment, and the influence of economic factors. The technology for preparing maleic anhydride by oxidizing n-butane gradually becomes a main route of maleic anhydride production due to the advantages of low raw material price, relatively light pollution, high carbon atom utilization rate, low maleic anhydride production cost and the like.
Currently, researchers have made extensive research and attempts on catalyst materials for the oxidation of n-butane to maleic anhydride, and vanadium-phosphorus-oxygen (VPO) catalysts are considered to be the most effective catalyst systems to date. There are a lot of publications and patent technologies on the preparation method of VPO catalyst, and it is summarized that VPO catalyst mainly focused on industrialization is usually prepared by using aqueous solvent or organic solvent method to prepare precursor, and the obtained precursor is calcined, activated and shaped to obtain final catalyst. The organic solvent method has certain advantages because the organic solvent method has larger specific surface area compared with the catalyst obtained by the aqueous phase method. The method mainly uses a single or mixed system of isobutyl alcohol and benzyl alcohol as a solvent. Therefore, the specific preparation process of the organic solvent method is to dissolve a vanadium source in an organic solvent, stir and reflux for reaction, add a phosphorus source, continue refluxing to obtain a precursor, and finally perform heat treatment and activation to obtain the catalyst.
The existing vanadium phosphorus oxygen catalyst has various structures, such as a sheet shape, a clover shape and the like. However, conventional methods for preparing these catalyst structures have a problem that the resulting structures have weak lateral compressive strength. The lateral compressive strength refers to a force required to crush a structure. The lateral compressive strength is an important indicator in the catalyst manufacturing process. Because the catalyst is subjected to a certain degree of pressure in the reaction process of heat treatment activation, packaging and transportation and installation in a reactor, if the lateral pressure is too weak, the wear rate of the catalyst is higher. The attrition rate is the mass of a unit mass of catalyst lost as a result of attrition. Catalysts with weaker lateral compressive strength wear more rapidly during the above process, and catalyst fragments or particles from attrition can greatly increase the pressure drop during operation of an industrial reactor, adversely affecting production.
In order to solve the important problem of weak lateral compressive strength, the method is generally realized by increasing the catalyst forming pressure, so that the compressive strength of the catalyst is indeed improved to a certain extent, but the increase of the forming pressure obviously improves the density of the catalyst, so that the bulk density of the catalyst is improved, and the specific surface area is reduced. The decrease in specific surface area not only results in a decrease in relative activity of the catalyst, thereby decreasing productivity, but also causes difficulties in heat dissipation of the reaction, causing a problem of high hot spots of the reaction.
Patent CN102325593A discloses a VPO catalyst molded body in a sheet form prepared by mixing a catalyst precursor with a lubricant based on graphite. The specific pore volume PV (mL/g) of the catalyst molded body, the bulk density rho (kg/L) of the catalyst molded body, and the geometric surface area A geometry (mm) of the catalyst molded body2) And geometric volume V geometry (mm)3) The following conditions are satisfied: 0.275 < PV.rho.A geometry/V geometry, the pressure loss caused by the shaped catalyst bodies is low.
Patent WO2010/047949a1 proposes a method of forming a clover-leaf catalyst construction having a cylinder radius and a leaf radius of about 6.25 and having an abrasion rate of about less than 10% and a lateral compressive strength of greater than 20 pounds, the abrasion rate being reduced by about 40% relative to before.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, a catalyst structure is low in lateral compressive strength and high in wear rate, and discloses a catalyst for preparing maleic anhydride by oxidizing n-butane.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
The invention aims to solve the third technical problem and provide a method for improving the yield of maleic anhydride prepared by oxidizing n-butane, which corresponds to one of the technical problems.
In order to solve one of the above technical problems, the technical solution disclosed by the present invention is: a catalyst for preparing maleic anhydride by oxidizing n-butane, which has a rose flower type structure; the main body of the catalyst comprises a vanadium source compound, a phosphorus source compound and an oxygen source compound, and is assisted by a trace amount of metal auxiliary agent; according to the total weight of the catalyst, the catalyst contains 26-35% of vanadium, 14-20% of phosphorus and 30-50% of oxygen; 0.02-7% of metal additive.
In the technical scheme, the catalyst for preparing the maleic anhydride by oxidizing the n-butane is characterized in that the vanadium element is at least one selected from refined ammonium metavanadate, vanadium pentoxide or organic acid vanadium; the metal auxiliary agent is at least one of cobalt, molybdenum, bismuth, sodium and zirconium.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a catalyst for preparing maleic anhydride by n-butane oxidation mainly comprises the following steps: firstly, mixing a metal additive and an organic solvent, then adding a vanadium source compound, then adding a phosphorus source compound, heating and refluxing for 6-18h under continuous stirring, filtering and drying the obtained product to obtain solid, drying to obtain VPO catalyst precursor powder, and carrying out heat treatment at the temperature of 300 ℃ and 500 ℃ to obtain the catalyst.
In the technical scheme, the particle size of the vanadium source compound is 1.5-3.5 mu m. The P/V ratio of the phosphorus source compound to the vanadium source compound is 0.8-1.3; the organic solvent required is an alcohol solvent having reducing ability.
In the technical scheme, the preparation method of the catalyst for preparing maleic anhydride by oxidizing n-butane is characterized in that the precursor powder and the lubricant are uniformly mixed to obtain a mixture A; placing the mixture A in a constant-temperature constant-humidity oven, and treating for 3-24 hours, wherein the constant-temperature is 20-60 ℃, and the constant-humidity is 40-95% of relative humidity; carrying out primary tabletting treatment by using an FYD type powder tabletting machine under the pressure of 10-40 MPa to obtain a primary molded catalyst; crushing and screening the once-formed catalyst, and taking the catalyst with the particle size of 20-160 meshes as pre-granulated particles; placing the pre-granulated particles on a rotary tablet press for secondary tabletting treatment to obtain a hollow cylindrical catalyst structure with the height of 4-6 mm; placing the catalyst structure in 380-500 ℃ and activating atmosphere for heat treatment activation; the activating atmosphere is selected from at least one of light hydrocarbon, air, inert gas, water vapor or carbon dioxide; the lubricant is selected from graphite, talcum powder and stearate, and the mass ratio of the lubricant to the precursor powder is 1-8: 100. The lubricant is preferably graphite.
In the technical scheme, a pore-forming agent is added into the mixture A and then the mixture A is subjected to constant temperature and humidity treatment, wherein the pore-forming agent is selected from at least one of stearic acid, soluble starch or sesbania powder. The preferable technical proposal is that the pore-forming agent is selected from stearic acid and soluble starch; more preferably, the pore-forming agent is selected from stearic acid, soluble starch and sesbania powder.
In the technical scheme, the pre-granulated particles are added with the pore-forming agent again and then subjected to rotary tabletting, wherein the pore-forming agent is selected from at least one of stearic acid, soluble starch or sesbania powder. The preferable technical proposal is that the pore-forming agent is selected from stearic acid and soluble starch; more preferably, the pore-forming agent is selected from stearic acid, soluble starch and sesbania powder.
In the technical scheme, the pressure range of the primary tabletting treatment is 15-30 MPa.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the method for preparing maleic anhydride by improving oxidation of n-butane adopts any one catalyst, and is characterized in that the catalyst reacts with butane raw material with the molar concentration of 1-1.5 mol% in a fixed bed reactor to produce the maleic anhydride, and the reaction process conditions are as follows: the space velocity is 1000-3000 hr-1The reaction temperature is 300-500 ℃, and the reaction pressure is normal pressure.
By adopting the technical scheme of the invention, the catalyst precursor is treated under the conditions of constant temperature and constant humidity, and the catalyst with high lateral compressive strength and low wear rate of the structure is obtained after secondary tabletting is carried out under the condition of secondary pore-forming agent addition. The prepared catalyst greatly improves the catalytic performance of the catalyst, the butane conversion rate reaches 88%, the maleic anhydride selectivity exceeds 60%, meanwhile, the lateral compressive strength of the catalyst structure exceeds 110N/cm, and the loss rate is lower than 8% after 600h reaction.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Detailed Description
[ example 1 ]
0.5g of cobalt oxalate was mixed with 120mL of benzyl alcohol and 360mL of isobutanol, then 5 was addedAdding 0.4g of vanadium pentoxide into 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, and fully and uniformly mixing 50g of precursor smaller than 200 meshes with 1.5g of graphite powder to form a mixture A; treating the mixture A in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85% for 12 hours; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; transferring the pre-granulated particles to a rotary tablet press, wherein the height of the catalyst structure is 5mm, so as to obtain the catalyst structure, the lateral compressive strength is 132N/cm, and the wear rate is 2.3%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of evaluation in a fixed bed reactor at a space velocity and a temperature of 400 ℃ under normal pressure show that the butane conversion rate is 81.6% and the yield of maleic anhydride is 50.3%, and the evaluation results are shown in Table 1.
[ example 2 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; adding 5g of pore-forming agent stearic acid into the mixture A, and treating for 12h in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85%; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; transferring the pre-granulated particles to a rotary tablet press, wherein the height of the catalyst structure is 6mm, so as to obtain the catalyst structure, the lateral compressive strength is 118N/cm, and the wear rate is 3.6%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of the evaluation of the space velocity and the atmospheric pressure at 400 ℃ in a fixed bed reactor show that the butane conversion rate is 90.3 percent and the yield of the maleic anhydride is 58.7 percent, and the evaluation results are detailed in Table 1.
[ example 3 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; treating the mixture A in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85% for 12 hours; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking 80-140 meshes of the mixture as pre-granulation particles; adding 5g of pore-forming agent stearic acid into the pre-granulated particles, transferring the pre-granulated particles onto a rotary tablet press, wherein the height of the catalyst structure is 5mm, so as to obtain the catalyst structure, the lateral compressive strength is 102N/cm, and the wear rate is 6.4%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of evaluation in a fixed bed reactor at a space velocity and a temperature of 400 ℃ under normal pressure show that the butane conversion rate is 89.8 percent and the yield of the maleic anhydride is 58.4 percent, and the evaluation results are detailed in Table 1.
[ example 4 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; adding 2.5g of pore-forming agent stearic acid into the mixture A, and treating for 12h in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85%; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; adding 2.5g of pore-forming agent stearic acid into the pre-granulated particles again, transferring the pre-granulated particles onto a rotary tablet press, wherein the height of the catalyst structure is 4mm, and obtaining the catalyst structure, the lateral compressive strength of which is 107N/cm, and the wear rate of which is 3.8%; the resulting catalyst was reacted with butane feed at a molar concentration of 1.5 mol%The reaction process conditions are as follows: 2000hr-1The results of evaluation in a fixed bed reactor at a space velocity and a temperature of 400 ℃ under normal pressure show that the butane conversion rate is 89.9 percent and the yield of the maleic anhydride is 58.6 percent, and the evaluation results are detailed in Table 1.
[ example 5 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; adding 2.5g of pore-forming agent soluble starch into the mixture A, and treating for 12h in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85%; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; adding 2.5g of pore-forming agent soluble starch into the pre-granulated particles again, transferring the mixture to a rotary tablet press, wherein the height of the catalyst structure is 5mm, so as to obtain the catalyst structure, the lateral compressive strength is 116N/cm, and the wear rate is 3.7%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The space velocity and the normal pressure of 400 ℃ are evaluated in a fixed bed reactor, the butane conversion rate is measured to be 84.8 percent, the yield of the maleic anhydride is measured to be 55.2 percent, and the evaluation results are detailed in the table 1.
[ example 6 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; adding 2.5g of a pore-forming agent sesbania powder into the mixture A, and treating for 12h in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85%; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; mixing the above extractsAdding 2.5g of sesbania powder serving as a pore-forming agent into the granulated particles again, transferring the granules to a rotary tablet press, wherein the height of the catalyst structure is 5mm, and obtaining the catalyst structure, wherein the lateral compressive strength is 120N/cm, and the wear rate is 3.5%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of the evaluation of the space velocity and the atmospheric pressure at 400 ℃ in a fixed bed reactor show that the butane conversion rate is 84.0 percent and the yield of the maleic anhydride is 54.9 percent, and the evaluation results are detailed in Table 1.
[ example 7 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; adding 2.5g of pore-forming agent stearic acid into the mixture A, and treating for 12h in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85%; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; adding 2.5g of pore-forming agent soluble starch into the pre-granulated particles again, transferring the mixture to a rotary tablet press, wherein the height of the catalyst structure is 5mm, so as to obtain the catalyst structure, the lateral compressive strength is 113N/cm, and the wear rate is 2.5%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of evaluation in a fixed bed reactor at a space velocity and a temperature of 400 ℃ under normal pressure show that the butane conversion rate is 89.2 percent and the yield of the maleic anhydride is 58.2 percent, and the evaluation results are detailed in Table 1.
[ example 8 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; mixing the above mixtureAdding 2.5g of pore-forming agent stearic acid into the A, and treating the mixture in a constant-temperature constant-humidity oven at the temperature of 30 ℃ and the equivalent humidity of 85% for 12 hours; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; adding 2.5g of a pore-forming agent sesbania powder into the pre-granulated particles again, transferring the mixture to a rotary tablet press, wherein the height of the catalyst structure is 5mm, so as to obtain the catalyst structure, the lateral compressive strength is 116N/cm, and the wear rate is 2.4%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of the evaluation of the space velocity and the atmospheric pressure at 400 ℃ in a fixed bed reactor show that the butane conversion rate is 87.1 percent and the yield of the maleic anhydride is 54.3 percent, and the evaluation results are detailed in Table 1.
[ example 9 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; adding 2.5g of pore-forming agent soluble starch into the mixture A, and treating for 12h in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85%; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; adding 2.5g of pore-forming agent stearic acid into the pre-granulated particles again, transferring the pre-granulated particles onto a rotary tablet press, wherein the height of the catalyst structure is 5mm, and obtaining the catalyst structure, the lateral compressive strength is 109N/cm, and the wear rate is 3.2%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of the evaluation of the space velocity and the atmospheric pressure at 400 ℃ in a fixed bed reactor show that the butane conversion rate is 87.5 percent and the yield of the maleic anhydride is 56.4 percent, and the evaluation results are detailed in Table 1.
[ example 10 ]
0.5g of cobalt oxalate, 120mL of benzyl alcohol and 360mL of isobutanol are mixed, 50.4g of vanadium pentoxide and 65mL of phosphoric acid are addedHeating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, and fully and uniformly mixing 50g of precursor smaller than 200 meshes with 1.5g of graphite powder to form a mixture A; adding 2.5g of a pore-forming agent sesbania powder into the mixture A, and treating for 12h in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85%; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; adding 2.5g of pore-forming agent stearic acid into the pre-granulated particles again, transferring the pre-granulated particles onto a rotary tablet press, wherein the height of the catalyst structure is 5mm, and obtaining the catalyst structure, wherein the lateral compressive strength is 111N/cm, and the wear rate is 3.0%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of the evaluation of the space velocity and the atmospheric pressure at 400 ℃ in a fixed bed reactor show that the butane conversion rate is 86.8 percent and the yield of the maleic anhydride is 54.7 percent, and the evaluation results are detailed in Table 1.
[ example 11 ]
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; adding 2g of pore-forming agent stearic acid into the mixture A, and treating for 12h in a constant-temperature constant-humidity oven with the temperature of 30 ℃ and the equivalent humidity of 85%; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking a part of 80-140 meshes; adding 1.5g of pore-forming agent soluble starch and 1.5g of sesbania powder into the pre-granulated particles again, transferring the mixture to a rotary tablet press, wherein the height of the catalyst structure is 5mm, and obtaining the catalyst structure, wherein the lateral compressive strength is 117N/cm, and the wear rate is 2.1%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The space velocity and the normal pressure of 400 ℃ are evaluated in a fixed bed reactor, and the butane conversion rate is measured to be89.2 percent and the yield of the maleic anhydride is 58.8 percent, and the evaluation results are detailed in table 1.
Comparative example 1
Mixing 0.5g of cobalt oxalate with 120mL of benzyl alcohol and 360mL of isobutanol, then adding 50.4g of vanadium pentoxide and 65mL of phosphoric acid, heating and refluxing for 16h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, screening the powdery catalyst precursor, taking 50g of precursor with the particle size of less than 200 meshes, and fully and uniformly mixing the precursor with 1.5g of graphite powder to form a mixture A; drying the mixture A in a blast oven at the temperature of 120 ℃ for 12 hours; then tabletting under the pressure of 20MPa to obtain a one-step molded catalyst structure; then crushing and screening the mixture, and taking 80-140 meshes of the mixture as pre-granulation particles; transferring the pre-granulated particles to a rotary tablet press, wherein the height of the catalyst structure is 5mm, so as to obtain the catalyst structure, the lateral compressive strength is 96N/cm, and the wear rate is 8.8%; the obtained catalyst is reacted with butane raw material with the molar concentration of 1.5 mol%, and the reaction process conditions are as follows: 2000hr-1The results of the evaluation of the space velocity and the atmospheric pressure at 400 ℃ in a fixed bed reactor show that the butane conversion is 84.5% and the yield of the maleic anhydride is 52.3%, and the evaluation results are shown in Table 1.
TABLE 1
Figure GDA0002611586470000091
Figure GDA0002611586470000101

Claims (9)

1. A preparation method of a catalyst for preparing maleic anhydride by n-butane oxidation is characterized by mainly comprising the following steps: firstly, mixing a metal additive with an organic solvent, wherein the metal additive is selected from cobalt, then adding a vanadium source compound, then adding a phosphorus source compound, heating and refluxing for 6-18h under continuous stirring, filtering and drying the obtained product to obtain VPO catalyst precursor powder, and uniformly mixing the precursor powder with a lubricant to obtain a mixture A; adding a pore-forming agent into the mixture A, and then carrying out constant-temperature and constant-humidity treatment for 3-24 hours, wherein the constant-temperature is 20-60 ℃, and the constant-humidity is 40-95% of relative humidity; carrying out primary tabletting treatment by using a powder tabletting machine under the pressure of 10-40 MPa to obtain a primary formed catalyst; crushing and screening the once-formed catalyst, and taking the catalyst with the particle size of 20-160 meshes as pre-granulated particles; and adding the pore-forming agent into the pre-granulated particles again, then placing the pre-granulated particles on a rotary tablet press for secondary tabletting treatment to obtain a hollow cylindrical catalyst structure with the height of 4-6 mm, and performing heat treatment at the temperature of 300-500 ℃ to obtain the catalyst.
2. The method for preparing a catalyst for preparing maleic anhydride by n-butane oxidation according to claim 1, wherein the particle size of the vanadium source compound is 1.5 to 3.5 μm.
3. The method for preparing a catalyst for producing maleic anhydride by n-butane oxidation according to claim 1, wherein the molar ratio of the phosphorus element to the vanadium element in the phosphorus source compound and the vanadium source compound is 0.8 to 1.3; the organic solvent is an alcohol solvent with reducing ability.
4. The method for producing a catalyst for producing maleic anhydride by n-butane oxidation according to claim 1, wherein the catalyst structure is subjected to heat treatment activation at a temperature of 380 to 500 ℃ in an activation atmosphere; the activating atmosphere is selected from at least one of light hydrocarbon, air, inert gas, water vapor or carbon dioxide; the lubricant is selected from graphite, talcum powder and stearate.
5. The method of preparing a catalyst for preparing maleic anhydride by n-butane oxidation according to claim 1, wherein the pore-forming agent is at least one selected from stearic acid, soluble starch, sesbania powder, and polyethylene glycol.
6. The method for preparing a catalyst for preparing maleic anhydride by n-butane oxidation according to claim 5, wherein the pore-forming agent is at least one selected from stearic acid, soluble starch, and sesbania powder.
7. The method for preparing a catalyst for producing maleic anhydride by n-butane oxidation according to claim 1, wherein the pressure of the primary tableting treatment is in the range of 15 to 30 MPa.
8. A method for preparing maleic anhydride by oxidizing n-butane, wherein the catalyst obtained by the preparation method of any one of claims 1 to 7 is reacted with a butane raw material with a molar concentration of 1-1.5% in a fixed bed reactor to produce maleic anhydride, and the reaction process conditions are as follows: the space velocity is 1000-3000 hr-1The reaction temperature is 300-500 ℃, and the reaction pressure is normal pressure.
9. A catalyst for preparing maleic anhydride by oxidizing n-butane, which is obtained by the preparation method of any one of claims 1 to 7.
CN201610849412.1A 2016-09-23 2016-09-23 Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof Active CN107866245B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610849412.1A CN107866245B (en) 2016-09-23 2016-09-23 Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610849412.1A CN107866245B (en) 2016-09-23 2016-09-23 Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107866245A CN107866245A (en) 2018-04-03
CN107866245B true CN107866245B (en) 2020-11-03

Family

ID=61751445

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610849412.1A Active CN107866245B (en) 2016-09-23 2016-09-23 Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107866245B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111097465B (en) * 2018-10-25 2022-10-11 中国石油化工股份有限公司 Preparation method of vanadium phosphorus oxide catalyst
CN109569742B (en) * 2018-12-18 2022-06-28 商丘国龙新材料有限公司 Method for improving forming strength of catalyst, catalyst and application thereof
CN109939709B (en) * 2019-04-19 2022-04-22 武汉科林化工集团有限公司 Catalyst for preparing maleic anhydride by oxidizing n-butane and preparation method thereof
CN114433151B (en) * 2020-10-31 2024-02-13 中国石油化工股份有限公司 Vanadium phosphorus oxide catalyst and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1210761A (en) * 1997-06-26 1999-03-17 电化学工业有限公司(国际) Process for producing coated catalysts for synthesis of maleic anhydride by gas-phase oxidation
JP2002348107A (en) * 2001-05-30 2002-12-04 Tonen Chem Corp Intercalation complex and method for producing the same
CN105413725A (en) * 2014-09-09 2016-03-23 中国石油化工股份有限公司 Vanadium-phosphorus catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1210761A (en) * 1997-06-26 1999-03-17 电化学工业有限公司(国际) Process for producing coated catalysts for synthesis of maleic anhydride by gas-phase oxidation
JP2002348107A (en) * 2001-05-30 2002-12-04 Tonen Chem Corp Intercalation complex and method for producing the same
CN105413725A (en) * 2014-09-09 2016-03-23 中国石油化工股份有限公司 Vanadium-phosphorus catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN107866245A (en) 2018-04-03

Similar Documents

Publication Publication Date Title
CN107866245B (en) Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof
US5168090A (en) Shaped oxidation catalyst structures for the production of maleic anhydride
CN104185617B (en) Use the method for producing acrylic acid of fixed bed multitube reactor
US8507721B2 (en) Process for preparing acrylic acid from ethanol and formaldehyde
JP5222237B2 (en) Method and catalyst for producing alcohols
EP0641256B1 (en) Process for the transformation of vanadium/phosphorus mixed oxide catalyst precursors into active catalysts for the production of maleic anhydride
US4982020A (en) Process for direct hydrogenation of glyceride oils
CA2661157C (en) Improved maleic anhydride catalyst and method for its preparation
US20180297015A1 (en) Hydrogenation Catalyst And Process For Production Thereof By The Use Of Uncalcined Starting Material
KR20140024009A (en) Catalyst for producing acrylic acids and acrylates
CN107866248B (en) Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof
US4855273A (en) Acid-resistant catalysts for the direct hydrogenation of fatty acids to fatty alcohols
EP3142785A1 (en) Process for the production of alkenols and use thereof for the production of 1,3-butadiene
CN101678325A (en) Catalyst for producing of acrylic acid, method for producing acrylic acid using the catalyst and method for producing water-absorbent resin using the acrylic acid
CN102781580A (en) Process for preparing catalyst used in production of unsaturated aldehyde and/or unsaturated carboxylic acid by dehydration reaction of glycerin, and catalyst obtained
AU649748B2 (en) Shaped oxidation catalyst structures for the production of maleic anhydride
CN103201031A (en) Novel glycerol dehydration catalyst and production method therefor
CN101912779B (en) Catalyst for catalytic synthesis of N-methylpyrrolidine and application thereof
US9266095B2 (en) Hydrogenation catalysts with cobalt and alkaline-earth metal modified supports
Khallouk et al. Mechanosynthezized Zn3V2O8 Mixed Oxide as Efficient Catalyst of Xylose Conversion to Glycolic Acid in Water
CA3152991C (en) New catalyst system for producing maleic anhydride by means of the catalytic oxidation of n-butane
CN114728864B (en) Process for producing dienes
KR101436146B1 (en) Catalyst system for producing acrolein from glycerol and the method of producing acrolein by using said catalyst system
CN114450081A (en) Reactor system for the preparation of maleic anhydride by catalytic oxidation of n-butane
KR20140076304A (en) A process for preparing 1,5-pentanediol and δ-valerolactone from tetrahydrofurfuryl alcohol

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant