CN116078368A - Catalyst for unsaturated olefin catalytic synthesis of unsaturated nitrile, preparation and application thereof - Google Patents

Catalyst for unsaturated olefin catalytic synthesis of unsaturated nitrile, preparation and application thereof Download PDF

Info

Publication number
CN116078368A
CN116078368A CN202111303898.6A CN202111303898A CN116078368A CN 116078368 A CN116078368 A CN 116078368A CN 202111303898 A CN202111303898 A CN 202111303898A CN 116078368 A CN116078368 A CN 116078368A
Authority
CN
China
Prior art keywords
catalyst
silicon
solution
precursor
containing carrier
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.)
Pending
Application number
CN202111303898.6A
Other languages
Chinese (zh)
Inventor
张奇
李静霞
张顺海
周晓峰
万里
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 CN202111303898.6A priority Critical patent/CN116078368A/en
Publication of CN116078368A publication Critical patent/CN116078368A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a catalyst for catalyzing unsaturated olefin to synthesize unsaturated nitrile, which comprises a silicon-containing carrier and an active component, wherein the active component comprises one or more of an oxide and/or cationic salt of a metal A, an oxide and/or cationic salt of an element B, an oxide and/or cationic salt of a rare earth element C, an oxide, cationic salt and oxyacid salt of a high-valence metal D, an oxide and/or cationic salt of Fe and Bi, and an oxide and/or oxyacid salt of Mo.

Description

Catalyst for unsaturated olefin catalytic synthesis of unsaturated nitrile, preparation and application thereof
Technical Field
The invention relates to a catalyst for catalyzing unsaturated olefin to synthesize unsaturated nitrile, and preparation and application thereof.
Background
Unsaturated nitrites represented by acrylonitrile are used as important chemical raw materials, and fluidized bed ammoxidation processes are widely adopted at present, wherein the catalyst is used as one of core technologies of the processes, and research and improvement on the catalyst are never interrupted. Currently, mo—bi based catalysts have been widely used industrially as relatively mature ammoxidation catalysts. For example, CN103769138A discloses a propylene ammoxidation catalyst having better acrylonitrile selectivity and more stable acrylonitrile single pass yield at temperatures around 430 ℃.
The load (WWH) of the catalyst, namely the ton of propylene which can be processed per ton of catalyst per hour, can be increased, the catalyst loading in the reactor can be reduced under the same capacity, and the catalyst has important significance for reducing the design size of a large-scale device and expanding the prior device, and is an important trend of the development of the acrylonitrile catalyst at present. However, with increasing catalyst loading, the reactor feed rate increases, the operating linear velocity increases correspondingly, and a faster operating linear velocity causes increased catalyst attrition, thus placing higher demands on catalyst attrition resistance. Meanwhile, the ammonia oxidation reaction of propylene is a strong exothermic reaction, the higher load can increase the reaction heat release amount in unit space, and the huge heat released by the reaction needs to be conducted outside the reactor, so that the heat conduction efficiency of the carrier is also highly required. The existing catalyst can not completely meet the requirements under high load conditions due to wear resistance and heat conduction efficiency, and the problem that the acrylonitrile yield is rapidly reduced and the stability is poor is easily generated when the catalyst is used under the high load conditions, so that further improvement is still needed.
CN1600423 and CN1600422 disclose that in the catalyst preparation process, 2-25% of solid silica with particle size of 5-100 nm is added into carrier initial silica sol to improve catalyst performance, and the attrition rate of catalyst is about 1.8-2.8%.
CN107282063B, CN107282060B, CN107282065B and CN107282094B disclose that adding certain amounts of zirconia, titania, diatomaceous earth, ZSM-5 molecular sieves as support modifiers during catalyst preparation can improve the selectivity and stability of the catalyst in propylene ammoxidation reactions, but the catalyst evaluation is also performed under lower loading conditions.
It is generally considered that the proper increase of the specific surface area and pore diameter of the catalyst is beneficial to promoting the adsorption and desorption of the substrate and the product, improving the mass transfer characteristic of the catalyst, and the larger pore volume is beneficial to heat transfer, thus having important significance for promoting the heat conduction efficiency of the catalyst. However, the larger pore diameter in the catalyst tends to reduce the structural strength of the catalyst, so that the attrition resistance and the stability of the finished catalyst are reduced. These methods show that the catalyst performance can be improved to a certain extent by introducing proper elements or adding proper modifiers, but the problems of low acrylonitrile yield and poor stability of the existing propylene ammoxidation catalyst under high load conditions are not solved.
Disclosure of Invention
The invention aims to solve the problems of low target product yield and poor stability of a catalyst for ammoxidation reaction under high load conditions in the prior art, and provides an ammoxidation catalyst which has larger pore diameter and specific surface area, better wear resistance, higher unsaturated alkene ammoxidation activity and unsaturated nitrile selectivity in ammoxidation reaction such as unsaturated alkene ammoxidation reaction, and simultaneously can maintain higher single pass yield of unsaturated nitrile for a long time under high load conditions.
The aim of the invention is achieved by the following technical scheme.
In a first aspect, the invention provides a catalyst for the catalytic synthesis of unsaturated nitriles from unsaturated olefins, characterized in that it comprises a siliceous support and an active component comprising an oxide and/or cationic salt of metal A, an oxide and/or cationic salt of element B, an oxide and/or cationic salt of rare earth element C, one or more of an oxide, cationic salt, oxysalt of high valence metal D, an oxide and/or cationic salt of Fe, bi, and an oxide and/or oxysalt of Mo,
wherein, the metal A is selected from at least one of Na, K, rb and Cs, and the element B is selected from at least one of Ca, ba, mn, co, ni, zn, mg, al, cr, B and P; the high valence metal D is at least one selected from Zr (IV), ti (IV), V (V), nb (V) and W (IV).
The cation salt is a salt formed by taking the element as a cation and other anions, and the oxyacid salt is a salt formed by taking the element and oxygen as anions of oxyacids and other cations. For example, the cationic salts of Mo include salts of molybdenum nitrate, molybdenum sulfate, and the like, and the oxo acid salts of Mo are salts of sodium molybdate, potassium molybdate, ammonium molybdate, and the like.
Wherein, the metal A is selected from at least one of Na, K, rb and Cs, and the element B is selected from at least one of Ca, ba, mn, co, ni, zn, mg, al, cr, B and P; the high valence metal D is at least one selected from Zr (IV), ti (IV), V (V), nb (V) and W (IV). In some embodiments, the active ingredient has the general formula a a B b C c D d Fe e Bi f Mo 13.6 O x Preferably, the value range of a is 0.01-2.5; b has a value range of 1-15; c has a value range of 0.01-5; d has a value range of 0.1-5; e is 0.5-10; f has a value range of 0.01 to 3; x is the total number of oxygen atoms required to satisfy the valence of each element in the active component.
In some embodiments, the silicon-containing carrier is silica and the silicon-containing carrier is present in the catalyst in an amount of 30 to 60wt%, based on the total weight of the catalyst.
In some embodiments, the catalyst has a specific surface area of 30 to 70m 2 /g。
In some embodiments, the catalyst has an average pore diameter of 10 to 20nm.
In some embodiments, the catalyst has an average particle size of 20 to 80 μm.
In some embodiments, the attrition rate of the catalyst is from 0.5 to 1.5%.
In a second aspect, the invention provides a method for preparing a catalyst, comprising mixing and boiling a solution I and a solution II, wherein the solution I is an aqueous solution containing a Bi precursor, a Fe precursor, a metal A precursor, an element B precursor, a rare earth element C precursor and a silicon-containing carrier source I; the solution II is a solution containing a Mo precursor, a high-valence metal D precursor and a silicon-containing carrier source II.
In some embodiments, the Bi precursor, fe precursor, metal a precursor, element B precursor, rare earth element C precursor may be an oxide of the corresponding element or any substance that may form the oxide after firing, such as an oxide, hydroxide, inorganic acid salt, and organic acid salt of the corresponding element (including hydrates of these compounds), preferably water-soluble inorganic acid salts and water-soluble organic acid salts, more preferably halides, alkoxides, sulfates, nitrates, and acetates, most preferably nitrates; these precursors may be used alone or in combination of plural kinds in an arbitrary ratio.
In some embodiments, the solution II is a solution containing a Mo precursor, a high valence metal D precursor, and a silicon-containing carrier source II. The Mo precursor and the high-valence metal D precursor may be oxides of the corresponding elements or any substances that can form the oxides after firing, and may be oxides, hydroxides, inorganic acid salts, organic acid salts, ammonium salts of oxy acids, and the like of the corresponding elements, preferably one or more of water-soluble inorganic acid salts, water-soluble organic acid salts, or ammonium salts of oxy acids, and more preferably ammonium salts of oxy acids. Solution II solvents include any liquid used in the art to facilitate the mixing of the starting materials (e.g., precursors) in the synthesis of the catalyst, more particularly alcohols and/or water, especially C1-C6 monohydric alcohols and water, and more preferably water.
The process for preparing the catalyst according to the invention further comprises ageing the solutions I and II prior to mixing.
In some embodiments, further comprising spray drying and firing after the pulp cooking.
In some embodiments, the silicon-containing carrier source I is polysilicic acid and/or polysilicates, preferably polysilicic acid, preferably SiO contained in the silicon-containing carrier source 1 is added based on the total weight of the silicon-containing carrier 2 The weight is not more than 30wt%, more preferably not more than 15wt% of the total weight of the silicon-containing carrier.
In some embodiments, the silicon-containing carrier source II is at least one of silica sol, water glass, silica gel, and silicate.
In some embodiments, the polysilicic acid is typically prepared prior to use, for example, by passing a quantity of sodium silicate solution through a strong acid cation exchange resin column and adjusting the pH of the mixed solution by the addition of a dilute sulfuric acid solution. Polysilicic acid used in the present invention, siO thereof 2 The weight percentage concentration is 1-10wt% and the pH value range is 2-6.
In some embodiments, the total solute content of solution I is 20-40wt%.
In some embodiments, the total solute content of solution II is from 30 to 80wt%.
In some embodiments, the aging conditions include: the temperature is 10 to 50℃and preferably 20 to 40 ℃.
In some embodiments, the aging conditions include: the time is 0.1 to 12 hours, preferably 0.5 to 3 hours.
In some embodiments, the aging conditions include: the stirring speed is 200 to 800rpm, preferably 250 to 450rpm, more preferably 300 to 400rpm.
The aging is advantageous in that the catalyst has high activity of ammoxidation of unsaturated olefin and selectivity of unsaturated nitrile, and also has good abrasion resistance.
In some embodiments, the cooking conditions comprise: the temperature is 10 to 80℃and preferably 45 to 70 ℃.
In some embodiments, the cooking conditions comprise: the time is 0.1 to 3 hours, preferably 0.5 to 1.5 hours.
In some embodiments, the cooking conditions comprise: the stirring speed is 200 to 1000rpm, preferably 250 to 500rpm, more preferably 250 to 350rpm.
In some embodiments, the spray drying conditions include: the drying heat source is air.
In some embodiments, the spray drying conditions include: the drying temperature is 250 to 400 ℃, preferably 300 to 350 ℃.
In some embodiments, the spray drying conditions include: the drying time is 0.5 to 3 hours, preferably 0.5 to 1.5 hours.
In some embodiments, the spray drying conditions include: the average diameter of the spray droplets is 40 to 200. Mu.m, preferably 40 to 180. Mu.m.
In some embodiments, the firing conditions include: under an oxygen-containing atmosphere.
In some embodiments, the firing conditions include: the firing temperature is 200 to 750 ℃, preferably 300 to 700 ℃.
In some embodiments, the firing conditions include: the calcination time is 2 to 8 hours, preferably 3 to 6 hours.
According to the present invention, the content of oxygen in the oxygen-containing atmosphere is not particularly limited, and preferably the oxygen content in the oxygen-containing atmosphere is more than 0 and less than 80%, more preferably more than 0 and less than 50% by volume.
In a third aspect, the present invention provides the use of a catalyst for the ammoxidation of an unsaturated olefin to produce an unsaturated nitrile.
In some embodiments, the unsaturated olefin is a C2-C5 unsaturated olefin.
In some embodiments, in the ammoxidation of propylene to acrylonitrile.
In some embodiments, propylene undergoes ammoxidation in the presence of molecular oxygen, ammonia to produce acrylonitrile using the ammoxidation catalyst. According to the present invention, the specifications of propylene, molecular oxygen and ammonia are not particularly limited; although the low molecular saturated hydrocarbon content in the raw propylene has no effect on the reaction, the propylene concentration is preferably more than 85 mol% from the economical viewpoint; ammonia can be fertilizer grade liquid ammonia; the molecular oxygen required for the reaction may be pure oxygen, oxygen-enriched and air from a technical point of view, but air is preferred from an economical and safety point of view.
In some embodiments, to increase propylene conversion and acrylonitrile yield, the propylene: ammonia: the molar ratio of air is 1:1.0 to 1.5:8 to 10.5, preferably 1:1 to 1.3: 8.8-10.
In some embodiments, to increase propylene conversion and acrylonitrile yield, the ammoxidation conditions are: the reaction temperature is 400-470 ℃, preferably 410-450 ℃, the reaction pressure (gauge pressure) is 0.03-0.15 MPa, preferably 0.06-0.14 MPa, and the weight hourly space velocity is 0.045-0.15 h-1, preferably 0.06-0.13 h-1.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the ammoxidation catalyst provided by the invention, by adjusting the active metal component of the catalyst, zr (IV), ti (IV), V (V), nb (V), W (IV) and other elements with high valence states are introduced, so that the stability of the catalyst in roasting and use is enhanced, the sintering of the catalyst is prevented, the surface area of the catalyst is promoted, and the aperture of the catalyst is improved.
(2) Compared with the preparation method of the ammonia oxidation catalyst in the prior art, the preparation method of the improved ammonia oxidation catalyst uses two different silicon-containing carrier sources and respectively adds the two silicon-containing carrier sources into the solution through different steps, wherein the silicon-containing carrier sources I and Bi element precursors, fe element precursors, metal A element precursors, element B precursors and rare earth elementsAging the precursor of element C in water solution can produce stable polysilicate metal salt with even dispersion. The catalyst is favorable for maintaining the high surface area and uniform pore size distribution of the catalyst in the subsequent drying and roasting steps, and the average pore diameter of the catalyst can be kept between 10 and 20nm, so that the catalytic activity of the catalyst under high load is improved, and the comprehensive performance of the catalyst is improved. Further, by controlling the SiO in the added silicon-containing carrier source I 2 The weight of the catalyst accounts for the total weight of the silicon-containing carrier, so that the catalyst after spray drying is more uniform, has better adhesive effect, and can better improve the strength of the catalyst compared with the use of a single carrier source, thereby improving the wear resistance of the catalyst.
(3) The ammoxidation catalyst provided by the invention is applied to the preparation of unsaturated nitrile by ammoxidation of unsaturated olefin, has higher ammoxidation activity of unsaturated olefin and selectivity of unsaturated nitrile, has longer service life under high-load conditions, and can maintain higher single pass yield of unsaturated nitrile for a long time, thereby greatly improving the production efficiency and economy of unsaturated nitrile.
Reference numerals
FIG. 1 is a graph of nitrogen adsorption-desorption for the catalysts of example 1, comparative example 2;
FIG. 2 is a graph showing pore diameter distribution of the catalyst of example 1 and comparative example 2.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples and the accompanying drawings, which are given by way of illustration only and are not limiting the scope of application of the invention.
In the invention, the measurement method of the average particle size adopts a Markov MS2000 laser particle sizer for measurement. The refractive index of the catalyst is selected before the sample is measured, so that SiO 2 Is the refractive index of the catalyst sample. The background is measured before the sample is measured, the sample is added to 10% of the shading degree after the measurement, and the average value is selected after three measurements are carried out.
The method for measuring the specific surface area and the aperture adopts a Tristar physical adsorption instrument for measurement. Before the sample is tested, heating, vacuumizing and degassing are needed. The porosity was measured on the samples at 77K, the specific surface area was calculated by the Brunauer-Emmett-Teller (BET) method, and the pore size distribution and pore volume were calculated from isothermal adsorption branches using the Barrettner-Joyner-Halenda (BJH) model.
The method for testing the wear resistance of the invention comprises the steps of maintaining the pressure of a system to be 0.3MPa, sieving 50 g of catalyst samples with the particle size of 160-250 meshes loaded in a wearing instrument by using high-speed stable air flow through the wearing instrument, continuously blowing the catalyst samples into a flask extraction tube from a wearing area by using an elutriation method, and respectively weighing the mass of the catalyst in the flask extraction tube after 5 hours and 15 hours of continuous blowing, wherein the mass is W respectively 1 And W is 2 The attrition rate of the catalyst was calculated according to the following formula:
abrasion ratio (%) = (W) 2 -W 1 )/(50-W 1 )×100％
The activity evaluation of the catalyst in the present invention was carried out in a fluidized bed reactor having an inner diameter of 38 mm. 400 g of catalyst was charged, the molar ratio of propylene to ammonia to air was 1:1.25:9.7 at a reaction temperature of 430℃and a reaction pressure (gauge pressure) of 0.085MPa, and the weight hourly space velocity (WWH) was 0.095h -1 。
The conversion of propylene, the selectivity to acrylonitrile and the single pass yield were used as evaluation catalyst performance indices, which were defined as follows:
propylene conversion (%) = (moles of propylene consumed by reaction/moles of propylene fed) ×100%
Acrylonitrile selectivity (%) = (moles of acrylonitrile produced/moles of propylene consumed by the reaction) ×100%
Acrylonitrile single pass yield (%) = (moles of acrylonitrile produced/moles of propylene feed) ×100%
Example 1
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 2000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2250 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 56m 2 And/g, the average pore diameter is about 14.3nm, the distribution is uniform, the average particle size is 56 mu m, and the abrasion rate is 0.79%. The nitrogen adsorption-desorption graph of the catalyst is shown in fig. 1, and the pore size distribution graph of the catalyst is shown in fig. 2. As shown in fig. 1 and 2, the catalyst has a large average pore diameter and a large specific surface area.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 99.1%, the acrylonitrile selectivity is 85.1%, and the single pass yield of the acrylonitrile is 84.3%. The catalyst composition and performance evaluation parameters are shown in tables 1 and 2, and the rest of examples and comparative examples are the same.
Example 2 (SiO in the polysilicic acid added compared to example 1) 2 The mass accounts for 5wt% of the total mass of the carrier
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 1000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 5wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2375 g of silica sol with a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 49m 2 And/g, the average pore diameter is about 12.5nm, the distribution is uniform, the average particle size is 49 mu m, and the abrasion rate is 0.85%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 98.9%, the acrylonitrile selectivity is 84.5%, and the acrylonitrile single pass yield is 83.6%.
Example 3 (SiO in the polysilicic acid added compared to example 1) 2 The mass accounts for 15wt% of the total mass of the carrier
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O is dissolved in 100mL of water,then 1500 g of polysilicic acid solution having a weight concentration of 10wt% and a pH of 2.5 was added thereto, followed by aging at 35℃under stirring at 300rpm for 2 hours to obtain a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 15wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Thereafter, the mixed solution I, the mixed solution II and 2125 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm at a temperature of 65℃for 1.5 hours to cook the slurry, to obtain a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 53m 2 And/g, the average pore diameter is about 14.6nm, the distribution is uniform, the average particle size is 57 mu m, and the abrasion rate is 0.93%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 99.2%, the acrylonitrile selectivity is 85.3%, and the single pass yield of the acrylonitrile is 84.6%.
Example 4 (SiO in the polysilicic acid added compared to example 1) 2 The mass of the catalyst accounts for 25 weight percent of the total mass of the carrier
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, after which 2500 g of a polysilicic acid solution having a weight concentration of 10wt% and a pH of 2.5 was added, and then aged at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 25wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 1875 g of silica sol with a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm at a temperature of 65℃for 1.5 hours to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 34m 2 And/g, the average pore diameter is about 15.6nm, the distribution is uniform, the average particle size is 48 mu m, and the abrasion rate is 1.16%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 98.8%, the acrylonitrile selectivity is 84.3%, and the acrylonitrile single pass yield is 83.3%.
Example 5 (40 wt% of the total weight of the catalyst compared to example 1)
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, after which 1333.3 g of polysilicic acid solution having a weight concentration of 5wt% and a pH of 3 was added, and then aged at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then mixing the mixed solution I, the mixed solution II and 1500 g of silica sol with the weight concentration of 40wt percent, and then stirring at the temperature of 65 ℃ for 1.5h at the stirring speed of 300rpmA slurry was obtained. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst is 48m 2 And/g, the average pore diameter is about 12.7nm, the distribution is uniform, the average particle size is 56 mu m, and the abrasion rate is 1.64%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 98.0%, the acrylonitrile selectivity is 84.1%, and the acrylonitrile single pass yield is 82.4%. The catalyst composition and performance evaluation parameters are shown in tables 1 and 2, and the rest of examples and comparative examples are the same.
Example 6 (Sm replaces Nd and W replaces Zr compared with example 1)
91.0 g Bi (NO) 3 ) 3 ·5H 2 O, 363.5 g Ni (NO) 3 ) 2 ·6H 2 O, 181.9 g Co (NO) 3 ) 2 ·6H 2 O, 110.7 g Ca (NO) 3 ) 2 ·4H 2 O, 252.5 g Fe (NO) 3 ) 3 ·9H 2 O, 160.3 g of Mg (NO 3 ) 2 ·6H 2 O, 9.2 g RbNO 3 62.5 g Sm (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 2000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 750.4 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 81.6 g (NH) 4 ) 10 W 12 O 41 ·5H 2 O was dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2250 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particulate matter is treated in an oxygen-containing atmosphere (oxygen gasThe integration amount was 21%), and the catalyst was obtained by baking at 600℃for 4 hours. The specific surface area of the catalyst was 52m 2 And/g, the average pore diameter is about 13.8nm, the distribution is uniform, the average particle size is 57 mu m, and the abrasion rate is 0.87%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 99.0%, the acrylonitrile selectivity is 84.5%, and the acrylonitrile single pass yield is 83.9%.
Example 7 (different Co, ni, mg, zr content compared to example 1)
100.0 g Bi (NO) 3 ) 3 ·5H 2 O, 249.9 g Ni (NO) 3 ) 2 ·6H 2 O, 50.0 g Co (NO) 3 ) 2 ·6H 2 O, 121.8 g Ca (NO 3 ) 2 ·4H 2 O, 277.7 g Fe (NO) 3 ) 3 ·9H 2 O, 132.2 g of Mg (NO 3 ) 2 ·6H 2 O, 10.1 g RbNO 3 67.8 g Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 2000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 825.3 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 119.2 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2250 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst is 54m 2 And/g, the average pore diameter is about 14.2nm, the distribution is uniform, the average particle size is 58 mu m, and the abrasion rate is 0.93%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 99.0%, the acrylonitrile selectivity is 85.0%, and the single pass yield of the acrylonitrile is 84.1%.
Example 8 (in comparison with example 6, the preferred embodiment implementation was supplemented with an orthogonal experimental design)
98.8 g Bi (NO) 3 ) 3 ·5H 2 O, 246.8 g Ni (NO) 3 ) 2 ·6H 2 O, 49.4 g Co (NO) 3 ) 2 ·6H 2 O, 120.2 g Ca (NO) 3 ) 2 ·4H 2 O, 274.3 g Fe (NO) 3 ) 3 ·9H 2 O, 130.6 g of Mg (NO 3 ) 2 ·6H 2 O, 67.0 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 2000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 815.1 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 81.4 g TiOSO 4 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2250 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 51m 2 And/g, the average pore diameter is about 16.3nm, the distribution is uniform, the average particle size is 50 mu m, and the abrasion rate is 0.81%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 99.1%, the acrylonitrile selectivity is 84.3%, and the acrylonitrile single pass yield is 83.5%.
Example 9 (in comparison with example 6, the preferred embodiment implementation was supplemented with an orthogonal experimental design)
94.0 g Bi (NO) 3 ) 3 ·5H 2 O, 93.9 g Ni (NO) 3 ) 2 ·6H 2 O, 47.0 g Co (NO) 3 ) 2 ·6H 2 O, 114.4 g Ca (NO) 3 ) 2 ·4H 2 O, 522.0 g Fe (NO) 3 ) 3 ·9H 2 O, 82.8 g of Mg (NO 3 ) 2 ·6H 2 O, 81.6 g KNO 3 63.7 g Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 3000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours, to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 775.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 149.4 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 3375 g of silica sol with a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 59m 2 And/g, the average pore diameter is about 16.5nm, the distribution is uniform, the average particle size is 54 mu m, and the abrasion rate is 0.62%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 98.8%, the acrylonitrile selectivity is 84.5%, and the acrylonitrile single pass yield is 83.5%.
Example 10 (in comparison with example 6, the preferred embodiment implementation was supplemented with an orthogonal experimental design)
97.0 g Bi (NO) 3 ) 3 ·5H 2 O, 97.0 g Ni (NO) 3 ) 2 ·6H 2 O, 194.1 g Co (NO) 3 ) 2 ·6H 2 O, 118.1 g Ca (NO) 3 ) 2 ·4H 2 O, 404.2 g Fe (NO) 3 ) 3 ·9H 2 O, 89.5 g Mn (NO) 3 ) 2 13.0 g CsNO 3 65.8 g Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, after which 1333.3 g of polysilicic acid solution having a weight concentration of 5wt% and a pH of 3 was added, and then aged at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 800.7 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 43.5 g (NH) 4 ) 10 W 12 O 41 ·5H 2 O was dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 1500 g of silica sol with a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm at a temperature of 65℃for 1.5 hours to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 47m 2 And/g, the average pore diameter is about 13.8nm, the distribution is uniform, the average particle size is 61 mu m, and the abrasion rate is 0.86%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 99.2%, the acrylonitrile selectivity is 85.0%, and the single pass yield of the acrylonitrile is 84.3%.
Example 11 (SiO in the polysilicic acid added compared to example 1) 2 The mass accounts for 40wt% of the total mass of the carrier
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 4000 g of a polysilicic acid solution having a weight concentration of 10wt% and a pH of 2.5, followed by aging at 35℃with stirring at 300rpm for 2 hours, to give a mixed solution I. Added polysiliconeSiO contained in acid 2 The weight is 40wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 1500 g of silica sol with a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm at a temperature of 65℃for 1.5 hours to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst is 28m 2 And/g, the average pore diameter is about 11.6nm, the distribution is uniform, the average particle size is 48 mu m, and the abrasion rate is 1.23%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 98.3%, the acrylonitrile selectivity is 84.3%, and the single pass yield of the acrylonitrile is 82.9%.
Example 12 (in contrast to example 1, the aging conditions are not within the required range)
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 2000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 80℃with stirring at 400rpm for 3 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Thereafter, the mixed solution I, the mixed solution II and 2250 g of silicon having a weight concentration of 40wt%The sol was mixed and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst is 30m 2 And/g, the average pore diameter is about 9.5nm, the distribution is uniform, the average particle size is 47 mu m, and the abrasion rate is 1.42%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 98.6%, the acrylonitrile selectivity is 84.3%, and the single pass yield of the acrylonitrile is 83.1%.
Example 13 (compared to example 1, the cooking conditions were not within the required range)
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 2000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2250 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 4 hours at a temperature of 120℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained granules are subjected to an oxygen-containing atmosphere (oxygen volume fraction 21%) at 600 DEG CRoasting for 4 hours to obtain the catalyst. The specific surface area of the catalyst was 34m 2 And/g, the average pore diameter is about 10.2nm, the distribution is uniform, the average particle size is 49 mu m, and the abrasion rate is 1.35%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 98.7%, the acrylonitrile selectivity is 84.0%, and the single pass yield of the acrylonitrile is 82.9%.
Example 14 (in contrast to example 1, spray drying is not within the required range)
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 2000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2250 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 340 ℃, the drying time is 1h, and the average diameter of spray droplets is 250 mu m, so as to obtain the particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 33m 2 And/g, the average pore diameter is about 11.5nm, the distribution is uniform, the average particle size is 96 mu m, and the abrasion rate is 1.68%.
The activity evaluation of the catalyst showed that the propylene conversion of the catalyst was 97.3%, the acrylonitrile selectivity was 83.2% and the single pass yield of acrylonitrile was 81.0%.
Comparative example 1 (inapplicable polysilicic acid solution)
100.4 g Bi (NO) 3 ) 3 ·5H 2 O, 301.0 g Ni (NO) 3 ) 2 ·6H 2 O, 100.4 g Co (NO) 3 ) 2 ·6H 2 O, 122.2 g Ca (NO) 3 ) 2 ·4H 2 O, 278.8 g Fe (NO) 3 ) 3 ·9H 2 O, 88.5 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.1 g of Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 250 g of a silica sol having a weight concentration of 40wt%, followed by aging at a temperature of 35℃with stirring at 300rpm for 2 hours, to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 828.5 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 79.8 g ZrO (NO) 3 ) 2 Dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2250 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 340 ℃, the drying time is 1h, and the average diameter of spray droplets is 250 mu m, so as to obtain the particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst was 43m 2 And/g, the average pore diameter is about 9.1nm, the distribution is uniform, the average particle size is 62 mu m, and the abrasion rate is 1.43%. The nitrogen adsorption-desorption graph of the catalyst is shown in fig. 1, and the pore size distribution graph of the catalyst is shown in fig. 2. As shown in fig. 1 and 2, when the catalyst uses only silica sol as a silicon-containing carrier source, the catalyst pores have a smaller diameter and a lower specific surface, which is disadvantageous for diffusion of substrate and product molecules on the catalyst surface.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 97.6%, the acrylonitrile selectivity is 84.6%, and the acrylonitrile single pass yield is 82.6%.
Comparative example 2 (without adding any higher valent metal D)
100.6 g Bi (NO) 3 ) 3 ·5H 2 O, 301.4 g Ni (NO) 3 ) 2 ·6H 2 O, 100.5 g Co (NO) 3 ) 2 ·6H 2 O, 122.4 g Ca (NO) 3 ) 2 ·4H 2 O, 279.2 g Fe (NO) 3 ) 3 ·9H 2 O, 88.6 g of Mg (NO 3 ) 2 ·6H 2 O, 10.2 g RbNO 3 68.2 g Nd (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, followed by addition of 2000 g of a polysilicic acid solution having a weight concentration of 5wt% and a pH of 3, followed by aging at 35℃with stirring at 300rpm for 2 hours to give a mixed solution I. SiO contained in the added polysilicic acid 2 The weight is 10wt% of the total weight of the carrier. 829.6 g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 250mL of water to give a mixed solution II. Then, the mixed solution I, the mixed solution II and 2250 g of silica sol having a weight concentration of 40wt% were mixed, and then stirred at a stirring speed of 300rpm for 1.5 hours at a temperature of 65℃to cook the slurry, thereby obtaining a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 325 ℃, the drying time is 1h, and the average diameter of spray droplets is 120 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 4 hours at 600 ℃ in an oxygen-containing atmosphere (the oxygen volume fraction is 21%), and the catalyst is obtained. The specific surface area of the catalyst is 48m 2 And/g, the average pore diameter is about 13.6nm, the distribution is uniform, the average particle size is 58 mu m, and the abrasion rate is 1.65%.
The activity evaluation of the catalyst shows that the propylene conversion rate of the catalyst is 96.5%, the acrylonitrile selectivity is 83.2%, and the single pass yield of the acrylonitrile is 80.3%.
TABLE 1 ammoxidation catalyst composition and Properties
Figure BDA0003339425180000161
/>
TABLE 2 evaluation results of attrition rate and Activity of ammoxidation catalysts
Figure BDA0003339425180000171
From the results of examples 1 to 14 and comparative examples 1 and 2 described above, it is understood that by adding any of the D elements within the ranges specified in the present invention during the preparation of the ammoxidation catalyst and controlling the addition of the different siliceous carriers, the specific surface area and average pore diameter of the catalyst can be increased while maintaining a low attrition rate of the catalyst, so that the catalyst can maintain good mechanical stability under high load conditions, and a larger specific surface area is also advantageous for improving the heat transfer efficiency of the catalyst, thereby enabling the catalyst to exhibit a higher single pass yield level of acrylonitrile in the ammoxidation of propylene under high load conditions.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.

Claims (10)

1. A catalyst for the catalytic synthesis of unsaturated nitrile from unsaturated olefin is characterized by comprising a silicon-containing carrier and an active component, wherein the active component comprises one or more of oxide and/or cation salt of metal A, oxide and/or cation salt of element B, oxide and/or cation salt of rare earth element C, oxide, cation salt and oxyacid salt of high-valence metal D, oxide and/or cation salt of Fe and Bi, and oxide and/or oxyacid salt of Mo,
wherein, the metal A is selected from at least one of Na, K, rb and Cs, and the element B is selected from at least one of Ca, ba, mn, co, ni, zn, mg, al, cr, B and P; the high valence metal D is at least one selected from Zr (IV), ti (IV), V (V), nb (V) and W (IV).
2. The catalyst of claim 1 wherein the active component has the formula a a B b C c D d Fe e Bi f Mo 13.6 O x Preferably, the value range of a is 0.01-2.5; b has a value range of 1-15; c has a value range of 0.01-5; d has a value range of 0.1-5; e is 0.5-10; f has a value range of 0.01 to 3; x is the total number of oxygen atoms required to satisfy the valence of each element in the active component.
3. Catalyst according to claim 1 or 2, characterized in that the silicon-containing carrier is silica, the silicon-containing carrier being present in the catalyst in an amount of 30 to 60 wt.%, based on the total weight of the catalyst.
4. A catalyst according to any one of claims 1 to 3, wherein the specific surface area of the catalyst is 30 to 70m 2 /g; and/or an average pore diameter of 10 to 20nm; and/or an average particle size of 20 to 80 μm; and/or the abrasion rate is 0.5-1.5%.
5. The method for preparing the catalyst according to any one of claims 1 to 4, comprising mixing and boiling a solution I and a solution II, wherein the solution I is an aqueous solution containing a Bi precursor, a Fe precursor, a metal a precursor, an element B precursor, a rare earth element C precursor, and a silicon-containing carrier source I; the solution II is a solution containing a Mo precursor, a high-valence metal D precursor and a silicon-containing carrier source II.
6. The method of preparing a catalyst according to claim 5, further comprising aging the solution I and the solution II prior to mixing.
7. The method for preparing a catalyst according to claim 5 or 6, further comprising spray drying and calcination after the pulp cooking.
8. The method for preparing a catalyst according to any one of claims 5 to 7, wherein the silicon-containing carrier source I is polysilicic acid and/or polysilicic acidSalts, preferably polysilicic acid, preferably based on the total weight of the silicon-containing carrier, are added to the SiO contained in the silicon-containing carrier source 1 2 The weight is not more than 30wt%, more preferably not more than 15wt% of the total weight of the silicon-containing carrier; and/or the silicon-containing carrier source II is at least one of silica sol, water glass, silica gel and silicate.
9. The method for preparing a catalyst according to claim 7, wherein the aging conditions include: the temperature is 10-50 ℃, and/or the time is 0.1-12 h, and/or the stirring speed is 200-800 rpm;
and/or the cooking conditions include: the temperature is 10-80 ℃, and/or the time is 0.1-3 h, and/or the stirring speed is 200-1000 rpm;
and/or the spray drying conditions include: the drying heat source is air, the drying temperature is 250-400 ℃, the drying time is 0.5-3 h, and/or the average diameter of spray droplets is 40-200 mu m;
and/or the roasting conditions include: in an oxygen-containing atmosphere, the roasting temperature is 200-750 ℃ and/or the roasting time is 2-8 h.
10. Use of a catalyst according to any one of claims 1 to 4 or a catalyst prepared according to any one of claims 5 to 9 in the ammoxidation of an unsaturated olefin to produce an unsaturated nitrile, preferably of a C2 to C5 unsaturated olefin, preferably in the ammoxidation of propylene to acrylonitrile.
CN202111303898.6A 2021-11-05 2021-11-05 Catalyst for unsaturated olefin catalytic synthesis of unsaturated nitrile, preparation and application thereof Pending CN116078368A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111303898.6A CN116078368A (en) 2021-11-05 2021-11-05 Catalyst for unsaturated olefin catalytic synthesis of unsaturated nitrile, preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111303898.6A CN116078368A (en) 2021-11-05 2021-11-05 Catalyst for unsaturated olefin catalytic synthesis of unsaturated nitrile, preparation and application thereof

Publications (1)

Publication Number Publication Date
CN116078368A true CN116078368A (en) 2023-05-09

Family

ID=86204961

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111303898.6A Pending CN116078368A (en) 2021-11-05 2021-11-05 Catalyst for unsaturated olefin catalytic synthesis of unsaturated nitrile, preparation and application thereof

Country Status (1)

Country Link
CN (1) CN116078368A (en)

Similar Documents

Publication Publication Date Title
KR101399376B1 (en) Catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin
JP5907637B2 (en) Mesoporous composite oxide catalyst, production method thereof, and 1,3-butadiene synthesis method using the same
CN102451765A (en) Preparation method for composite oxide carrier
WO2013125389A1 (en) Method for producing 1,3-butadiene
CN101172240B (en) Method for preparing propylene by butylene disproportionation
CN103769148A (en) Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst
JP6017386B2 (en) Synthesis of butadiene from ethanol using metal-added SiO2-MgO catalyst prepared by hydrothermal synthesis
TW201726247A (en) Manufacturing method of fluid bed ammonia oxidation reaction catalyst and acrylonitrile that can be stably produced at high production rate and long term under condition of using no excessive ammonia
CN102451764A (en) Method for preparing zirconia-alumina composite oxide carrier
CN103071491B (en) Hydrogenation catalyst with large specific surface and low acid amount, and application thereof
CN107486197A (en) The preparation method of dehydrogenating low-carbon alkane microspherical catalyst
CN104707664A (en) Preparation method of alpha-alumina carrier for silver catalyst
US10919836B2 (en) Production method of aliphatic carboxylic acid ester
CN102451766A (en) Preparation method of composite oxide carrier
CN102451768A (en) Method for preparing zirconia-alumina composite oxide xerogel
EP3875446A1 (en) Method for producing alcohol and catalyst for producing alcohol
CN116078368A (en) Catalyst for unsaturated olefin catalytic synthesis of unsaturated nitrile, preparation and application thereof
CN107282063B (en) Acrylonitrile catalyst for propylene ammoxidation
CN102451769A (en) Preparation method of composite oxide adhesive
CN110732342A (en) Isobutane dehydrogenation catalyst with chlorite composite material with three-dimensional cubic and hexagonal pore channel structure as carrier and preparation method and application thereof
CN107282060B (en) Acrylonitrile catalyst for ammoxidation process
CN105642301B (en) A kind of preparation method for being used to synthesize the copper bismuth catalyst of 1,4 butynediols
CN103521235A (en) Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof
JP5020514B2 (en) Method for producing fluidized bed catalyst and method for producing nitriles
CN107282061B (en) Catalyst for preparing acrylonitrile by ammoxidation

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