CN111203251A - Wear-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon and preparation method thereof - Google Patents

Wear-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon and preparation method thereof Download PDF

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CN111203251A
CN111203251A CN202010120761.6A CN202010120761A CN111203251A CN 111203251 A CN111203251 A CN 111203251A CN 202010120761 A CN202010120761 A CN 202010120761A CN 111203251 A CN111203251 A CN 111203251A
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metal oxide
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邓忠华
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Dipp International Trade Dalian Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J35/615—100-500 m2/g
    • 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

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Abstract

The invention provides a wear-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon and a preparation method thereof. In addition, the catalyst has high density, can increase the density of a catalyst bed layer in the reactor, reduce the height of the bed layer, contribute to improving the space efficiency of the production process and reduce the production cost of products. The catalyst has high heat conduction efficiency, and the heat released in the reaction process can be quickly conducted out of the reactor, so that the accumulation of the reaction heat release is avoided, the fluctuation range of the reaction system is reduced, and the relative stability is kept.

Description

Wear-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon and preparation method thereof
Technical Field
The invention belongs to the technical field of molybdenum-based mixed metal oxides, and particularly relates to a wear-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon, which is particularly suitable for synthesizing at least one unsaturated nitrile in acrylonitrile and methacrylonitrile.
Background
The ammoxidation reaction refers to the reaction of at least one unsaturated nitrile of acrylonitrile and methacrylonitrile by reacting at least one of propylene, propane, isobutylene and isobutane with ammonia in the presence of molecular oxygen.
Since a large amount of heat is released in the ammoxidation process, propylene is subjected to ammoxidation to synthesize acrylonitrile, the heat release is 519KJ/mol, propane is subjected to ammoxidation to synthesize acrylonitrile, the heat release is 628KJ/mol, and the heat release of propane ammoxidation is about 20% more than that of propylene, a fluidized bed reactor is usually used to ensure uniform catalyst bed temperature, so that the size distribution and the shape of catalyst particles are suitable for flowing. In addition, in order to adapt to the catalyst in a fluidized state for stable use over a long period of time, the catalyst particles are required to have high abrasion resistance and high compressive strength. The catalysts synthesized by the conventional production method are loose particles with large pores, have poor wear resistance, and the bed density of the catalysts in the fluidized bed reactor is generally low, so that the production capacity of the reactor is limited. If the bed density of the catalyst is increased, the production capacity is improved, and the reaction heat release of unit space is increased, because the huge heat released by the reaction needs to be conducted to the outside of the reactor, the heat conduction efficiency of the carrier is also highly required. Although various catalyst developers have developed catalysts in which molybdenum-based mixed metal oxides are supported on a carrier such as silica, alumina, zirconia, titania, diatomaceous earth, molecular sieves, montmorillonite, etc., the problems of poor attrition resistance and low productivity of the existing catalysts have not been solved.
The density of the silicon carbide is 3.2g/cm3Specific silica (2.2 g/cm)3) The abrasive has high hardness, the Mohs hardness is 9.2-9.5, and the hardness of the abrasive is higher than that of corundum; the thermal conductivity is high and is 490W/mK, while the Mohs hardness of the commonly used silicon dioxide is 7.0 and the thermal conductivity is 7.6W/mK. The SiC has the advantages of wear resistance similar to that of diamond, good thermal stability, low density, high melting point, high strength, high elastic modulus, low thermal expansion coefficient, good chemical stability and the like, so that the silicon carbide becomes an ideal reinforcing agent for the composite material. Silicon carbide has been known to have a small specific surface area (<1m2In the case of a catalyst,/g) are not able to provide sufficient support sites for the catalytically active components, which is disadvantageous for the dispersion of the active components and is therefore unsuitable as a support for catalysts.
The ammoxidation of alkane to synthesize unsaturated nitrile has large heat release, and the problem of how to increase the production capacity of unit space and ensure the high-efficiency heat transfer is still the current one. The literature reports that nano silicon carbide is used as an unsaturated nitrile catalyst carrier.
Disclosure of Invention
In order to improve the unit space production capacity of the catalyst, the invention provides the novel wear-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon with high density, high heat conduction efficiency and good wear resistance and the preparation method thereof, so that the service life of the catalyst is prolonged, and the unit space production capacity of the catalyst is obviously improved.
The technical scheme adopted by the invention is as follows:
an abrasion-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of lower hydrocarbon is characterized in that: comprising a supported molybdenum-based mixed metal oxide having the formula:
Mo1VaMbNbcOd/40～60％wt-(eSiO2+fSiC)
wherein M is at least one of Te, Sb, Mn, Ag, Na, K, Rb, Cs, Mg, Ca, Sr, Fe, Co, Ce and Ni;
a is 0.05 to 1.0;
b is 0.005 to 1.0;
c is 0.05 to 1.0;
e is 0 to 0.9;
f is 0.1 to 1;
d is the number of oxygen atoms required to satisfy the oxidation state of the metal ion;
SiC is nano silicon carbide, and the specific surface area of the SiC is 100-300 m2/g。
The SiC is nano-microspheres.
Preferably, the attrition resistant mixed metal oxide catalyst further comprises a molybdate additive, said molybdate additive being a molybdate or a supported molybdate,
the chemical formula of the molybdate is as follows:
MaMobOx
wherein M is at least one of Be, Mg, Ca, Sr and Ba;
a is 0 to 10;
b is 1-10;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion;
the chemical formula of the supported molybdate is as follows:
MaMobOx/(40～80％)-SiC
wherein M is at least one of Be, Mg, Ca, Sr and Ba;
a is 1-10;
b is 1-10;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion;
the addition amount of the molybdate auxiliary agent is 0.05-10% of the total weight of the supported molybdenum-based mixed metal oxide.
The invention also provides a preparation method of the wear-resistant mixed metal oxide catalyst, which comprises the following steps:
s1 preparing an acidic aqueous solution of a metal source compound in the molybdenum-based mixed metal oxide;
s2, mixing the acidic aqueous solution with the dispersion liquid of silicon carbide in water to form slurry, or mixing the acidic aqueous solution, the dispersion liquid of silicon carbide in water and the dispersion liquid of silica sol in water to form slurry;
s3, grinding the slurry by a colloid mill, spray drying to form microspheres, and roasting to obtain the supported molybdenum-based metal oxide.
The preferred method of making the attrition resistant mixed metal oxide catalyst further includes S4 intimately mixing the above molybdate promoter (molybdate or supported molybdate) with a supported molybdenum-based mixed metal oxide to provide a catalyst containing a molybdate promoter; the addition amount of the molybdate auxiliary agent is 0.05-10% of the total weight of the supported molybdenum-based mixed metal oxide.
Preferably, the molybdate auxiliary agent is supported molybdate, and is obtained by loading a precursor compound of the molybdate auxiliary agent on a silicon carbide carrier by an impregnation method and roasting; the molybdate additive precursor compound comprises ammonium molybdate and alkaline earth metal salt, wherein the ammonium molybdate is one or more of ammonium heptamolybdate and ammonium tetramolybdate; the alkaline earth metal salt is one or more of magnesium nitrate, beryllium nitrate, calcium nitrate, strontium nitrate and barium nitrate.
The acid in the acidic aqueous solution in S1 is at least one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, lactic acid, oxalic acid, citric acid, malic acid, succinic acid, and tartaric acid.
The silica sol in S2 is alkaline silica sol with stable ammonia; the dispersion liquid of the silicon carbide in the water is formed by the nano silicon carbide in the water through at least one process of ultrasound and stirring.
In S3, the inlet temperature of a spray dryer is 180-300 ℃, and the outlet temperature is 100-150 ℃; the roasting process is to carry out denitration treatment for 1-3 hours at 200-400 ℃, and roast for 1-3 hours at 550-650 ℃.
The invention also provides the application of the wear-resistant mixed metal oxide catalyst, which is suitable for the reaction of synthesizing unsaturated nitrile by the ammoxidation of low-carbon hydrocarbon; the lower hydrocarbon is at least one of propylene, propane, isobutene and isobutane; the unsaturated nitrile is at least one of acrylonitrile and methacrylonitrile.
The beneficial results of the invention are: the micron silicon carbide has small specific surface area, can reduce the activity of the catalyst when used as a carrier, forms large holes and has poor wear resistance. The nano-scale inert silicon carbide is used as an atomic crystal and has the mechanical properties of high strength, high hardness, wear resistance, corrosion resistance and the like. Compared with micron silicon carbide, the silicon carbide composite material has the advantages of small particle size, capability of forming mesopores with silicon dioxide, large specific surface area, capability of providing enough loading sites for active components, no reduction of the activity of the catalyst and suitability for being used as a carrier of the catalyst. The catalyst prepared by using the nano silicon carbide or the mixture of the nano silicon carbide and the nano silicon dioxide as the carrier has the advantages of slightly improving the catalytic performance, obviously improving the wear resistance, greatly prolonging the service life of the catalyst and reducing the catalyst cost of the product. In addition, the catalyst has high density, can increase the density of a catalyst bed layer in the reactor, reduce the height of the bed layer, contribute to improving the space efficiency of the production process and reduce the production cost of products. The catalyst has high heat conduction efficiency, the heat released in the reaction process can be quickly conducted out of the reactor, the accumulation of the reaction heat release is avoided, the fluctuation range of the reaction system is reduced, the relative stability is kept, and the production capacity of unit space is increased. Is particularly suitable for the reaction of synthesizing unsaturated nitrile by the ammoxidation of low-carbon hydrocarbon with large air flow and large heat release. In addition, the mixed metal oxide catalyst containing the molybdate auxiliary agent and used for the reaction of synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon can obviously reduce the combustion amount of ammonia, so that the reaction system keeps higher oxygen content, organic byproducts are prevented from being polymerized and carbonized to block catalyst pore passages, reduction of high-valence metal ions in the catalyst is also inhibited, catalyst inactivation is prevented, the catalyst can keep high activity for a long time, and the industrial production of acrylonitrile can be ensured to be stably carried out for a long time. In addition, the silicon carbide supported molybdate auxiliary agent has better effect of reducing the ammonia combustion amount.
Detailed Description
The present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited by the examples, and those skilled in the art who have the above-mentioned disclosure will still be able to make some insubstantial modifications and adaptations to the present invention.
The catalytic reaction conditions are as follows:
catalyst loading: 380 g, the reaction temperature is 440 ℃, and the composition of the reaction gas is propane: ammonia gas: air 1:1:15, WWH 0.06, reaction pressure 0.08 MPa.
Abrasion index test
The attrition index of the ammoxidation catalyst was measured by a straight tube method for measuring the attrition index of the catalytic cracking catalyst, and the attrition index defined by the following equation was calculated.
AI(％)＝m2/(m-m1)×100
Wherein m is the mass (g) of the test sample;
m1a mass (g) of a sample scattered to the outside of the measurement system by abrasion within a period of 0 to 1 hour;
m2the mass (g) of the sample scattered to the outside of the measurement system was abraded within 1 to 5 hours.
Comparative example 1Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/50％wt-SiO2
Heating 400 ml of deionized water to 65 ℃, adding ammonium heptamolybdate (211.7 g), ammonium metavanadate (35.1 g) and antimony trioxide (45.5 g) under stirring to form a blue suspension, cooling to room temperature, adding silica sol (658 g, 40% wt of silicon dioxide) and hydrogen peroxide (60 g, 30% wt of hydrogen peroxide), and stirring for 1 hour to obtain a reaction mixture A.
150 ml of deionized water was heated to 65 ℃ and then niobium pentoxide hydrate (21.3 g, 75% wt niobium pentoxide), oxalic acid dihydrate (45.4 g), cerium ammonium nitrate (3.3 g) and magnesium nitrate hexahydrate (6.2 g) were added with stirring to form a colorless transparent solution which was allowed to cool to room temperature to give reaction mixture B.
The reaction mixtures a and B were mixed and stirred at 40-45 ℃ for 3 hours to form a final homogeneous catalyst precursor slurry.
The obtained catalyst precursor slurry is ground in a zirconia colloid mill for 15 to 30 minutes. The resulting slurry was then spray dried in a spray dryer at an inlet/outlet temperature of 220/120 ℃.
The resulting dried powder was subjected to denitration treatment at 280 ℃ for 1.5 hours and then calcined at 610 ℃ for 2 hours.
Comparative example 2 Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/50％wt-SiC
263.2 g of SiC (specific surface area 28 m)2/g) was dispersed ultrasonically in 320 ml of deionized water to form a homogeneous suspension. The procedure for preparing the dispersion of SiC was the same as in comparative example 1 except that the dispersion of SiC was used in place of the silica sol in comparative example 1.
Example 1Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/50％wt-SiC
263.2 g of SiC (specific surface area 120 m)2/g) was dispersed ultrasonically in 320 ml of deionized water to form a homogeneous suspension. The procedure for preparing the dispersion of SiC was the same as in comparative example 1 except that the dispersion of SiC was used in place of the silica sol in comparative example 1.
Example 2 Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/50％wt-SiC
263.2 g of SiC (specific surface area 150 m)2/g) was dispersed ultrasonically in 320 ml of deionized water to form a homogeneous suspension. The procedure for preparing the dispersion of SiC was the same as in comparative example 1 except that the dispersion of SiC was used in place of the silica sol in comparative example 1.
Example 3 Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/50％wt-SiC
263.2 g of SiC (specific surface area 180 m)2/g) was dispersed ultrasonically in 320 ml of deionized water to form a homogeneous suspension. The procedure for preparing the dispersion of SiC was the same as in comparative example 1 except that the dispersion of SiC was used in place of the silica sol in comparative example 1.
Example 4 Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/40％wt-SiO2+10％wt-SiC
52.6 g of SiC (specific surface area 150 m)2/g) was dispersed ultrasonically in 90 ml of deionized water to form a homogeneous suspension. This dispersion of SiC was thoroughly mixed with a silica sol (526.5 g, 40% by weight of silica) with stirring, and the procedure was otherwise the same as in comparative example 1, instead of the silica sol in comparative example 1.
Example 5 Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/30％wt-SiO2+20％wt-SiC
105.2 g of SiC (specific surface area 150 m)2/g) was dispersed ultrasonically in 150 ml of deionized water to form a homogeneous suspension. This SiC dispersion was thoroughly mixed with silica sol (395 g, 40% by weight of silica) in place of comparative example 1The silica sol of (1) was prepared in the same manner as in comparative example 1.
Example 6 Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/25％wt-SiO2+25％wt-SiC
131.6 g of SiC (specific surface area 150 m)2/g) was dispersed ultrasonically in 190 ml of deionized water to form a homogeneous suspension. This dispersion of SiC was thoroughly mixed with a silica sol (329 g, 40% by weight of silica) with stirring, and the procedure was otherwise the same as in comparative example 1, instead of the silica sol in comparative example 1.
Example 7 Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/20％wt-SiO2+30％wt-SiC
157.9 g of SiC (specific surface area 150 m)2/g) was dispersed ultrasonically in 230 ml of deionized water to form a homogeneous suspension. This dispersion of SiC was thoroughly mixed with a silica sol (263.3 g, 40% by weight of silica) with stirring, and the procedure was otherwise the same as in comparative example 1, instead of the silica sol in comparative example 1.
Example 8 Mo1V0.25Sb0.26Nb0.10Ce0.005Mg0.02On/10％wt-SiO2+40％wt-SiC
210.6 g of SiC (specific surface area 150 m)2/g) was dispersed ultrasonically in 280 ml of deionized water to form a homogeneous suspension. This dispersion of SiC was thoroughly mixed with a silica sol (131.5 g, 40% by weight of silica) with stirring, and the procedure was otherwise the same as in comparative example 1, instead of the silica sol in comparative example 1.
Example 9
The catalytic reaction results of the reactions for synthesizing acrylonitrile by ammoxidation of propane performed in the comparative examples 1-2 and the examples 1-8 are shown in table 1, and the catalyst obtained by using nano silicon carbide as a carrier has slightly improved catalytic performance and obviously reduced wear index, which indicates that the wear resistance of the catalyst is enhanced. At the same time, the compactness of the catalyst increases. In addition, the heat conduction efficiency of the catalyst is improved, heat can be effectively conducted, the service life of the catalyst is greatly prolonged, and the unit space production capacity of the catalyst is improved.
TABLE 1 comparative examples 1-2, examples 1-8 catalyst comparison
Figure BDA0002392900320000071
XC3: propane conversion; y isAN: the yield of acrylonitrile; sAN: acrylonitrile selectivity; y is-CN: the yield of the trinitrile is high.
Example 10
The catalyst is the catalyst obtained in example 1 and 0.5 percent of BeMoO in the total weight of the catalyst obtained in example 1 is added4(example 1Rb0.18Mg2.88Fe0.65Ni3.84Ce1.69Cr0.05Bi0.70Mo12O48.2950% wt-SiC catalyst 1 part and 0.005 part BeMoO4Mixed uniformly to obtain the mixed metal oxide catalyst).
Example 11
The catalyst is the catalyst obtained in example 2 and MgMoO which accounts for 0.5 percent of the total weight of the catalyst obtained in example 2 is added4。
Example 12
The catalyst is the catalyst obtained in example 3 and added with CaMoO accounting for 0.5 percent of the total weight of the catalyst in example 34。
Example 13
The catalyst was prepared by adding SrMoO in an amount of 0.5% by weight based on the total weight of the catalyst of example 4 to the catalyst obtained in example 44。
Example 14
The catalyst was prepared by adding BaMoO in an amount of 0.5% by weight based on the total weight of the catalyst of example 5 to the catalyst obtained in example 54。
Comparative example 3
The catalyst was prepared by adding 0.5% by weight of Li based on the total weight of the catalyst of example 6 to the catalyst obtained in example 62MoO4。
Example 15
The catalysts obtained in examples 10 to 14 and comparative example 3 were used to synthesize acrylonitrile by ammoxidation of propylene, and the results of the catalytic reactions are shown in Table 2.
TABLE 2 catalysts of examples 1-6, examples 10-14 and comparative example 3 comparative ammonia combustion
Figure BDA0002392900320000081
Figure BDA0002392900320000091
XC3＝: conversion of propylene; y isAN: the yield of acrylonitrile; sAN: acrylonitrile selectivity; y is-CN: the yield of the trinitrile is high.
Example 16
The catalyst is the catalyst obtained in example 2 and MgMoO which accounts for 0.1 percent of the total weight of the catalyst obtained in example 2 is added4。
Example 17
The catalyst is the catalyst obtained in example 2 and MgMoO which accounts for 0.3 percent of the total weight of the catalyst obtained in example 2 is added4。
Example 18
The catalyst is the catalyst obtained in example 2 and MgMoO is added in an amount of 1% of the total weight of the catalyst obtained in example 24。
Example 19
The catalyst is the catalyst obtained in example 2 and MgMoO which accounts for 5 percent of the total weight of the catalyst obtained in example 2 is added4。
Example 20
The catalysts obtained in examples 16 to 20 were subjected to a reaction for synthesizing acrylonitrile by ammoxidation of propylene, and the results of the catalytic reaction are shown in Table 3.
Table 3 comparison of the catalysts obtained in example 2, example 11 and 16 to 20 with ammonia combustion
Figure BDA0002392900320000092

Claims (9)

1. An abrasion-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of lower hydrocarbon is characterized in that: comprising a supported molybdenum-based mixed metal oxide having the formula:
Mo1VaMbNbcOd/40～60％wt-(eSiO2+fSiC)
wherein M is at least one of Te, Sb, Mn, Ag, Na, K, Rb, Cs, Mg, Ca, Sr, Fe, Co, Ce and Ni;
a is 0.05 to 1.0;
b is 0.005 to 1.0;
c is 0.05 to 1.0;
e is 0 to 0.9;
f is 0.1 to 1;
d is the number of oxygen atoms required to satisfy the oxidation state of the metal ion;
SiC is nano silicon carbide, and the specific surface area of the SiC is 100-300 m2/g。
2. The attrition resistant mixed metal oxide catalyst of claim 1, wherein the attrition resistant mixed metal oxide catalyst is selected from the group consisting of: the SiC is nano-microspheres.
3. The attrition resistant mixed metal oxide catalyst of claim 1, wherein the attrition resistant mixed metal oxide catalyst is selected from the group consisting of: also comprises a molybdate additive which is molybdate or supported molybdate,
the chemical formula of the molybdate is as follows:
MaMobOx
wherein M is at least one of Be, Mg, Ca, Sr and Ba;
a is 1-10;
b is 1-10;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion;
the chemical formula of the supported molybdate is as follows:
MaMobOx/(40～80％)-SiC
wherein M is at least one of Be, Mg, Ca, Sr and Ba;
a is 1-10;
b is 1-10;
x is the number of oxygen atoms required to satisfy the oxidation state of the metal ion;
the addition amount of the molybdate auxiliary agent is 0.05-10% of the total weight of the supported molybdenum-based mixed metal oxide.
4. A process for preparing an attrition resistant mixed metal oxide catalyst as claimed in claim 1 wherein: the method comprises the following steps:
s1 preparing an acidic aqueous solution of a metal source compound in the molybdenum-based mixed metal oxide;
s2, mixing the acidic aqueous solution with the dispersion liquid of silicon carbide in water to form slurry, or mixing the acidic aqueous solution, the dispersion liquid of silicon carbide in water and the dispersion liquid of silica sol in water to form slurry;
s3, grinding the slurry by a colloid mill, spray drying to form microspheres, and roasting to obtain the supported molybdenum-based mixed metal oxide.
5. The method of making an attrition resistant mixed metal oxide catalyst as recited in claim 4 wherein: the preparation method also comprises S4, wherein the molybdate auxiliary agent is obtained by fully mixing the molybdenum-based mixed metal oxide; the addition amount of the molybdate auxiliary agent is 0.05-10% of the total weight of the supported molybdenum-based mixed metal oxide.
6. The method of making an attrition resistant mixed metal oxide catalyst as recited in claim 5 wherein: the molybdate additive is supported molybdate, and is obtained by loading a precursor compound of the molybdate additive on a silicon carbide carrier by an impregnation method and roasting; the molybdate additive precursor compound comprises ammonium molybdate and alkaline earth metal salt, wherein the ammonium molybdate is one or more of ammonium heptamolybdate and ammonium tetramolybdate; the alkaline earth metal salt is one or more of magnesium nitrate, beryllium nitrate, calcium nitrate, strontium nitrate and barium nitrate.
7. The method of making an attrition resistant mixed metal oxide catalyst as claimed in claim 4 or 5 wherein: the acid in the acidic aqueous solution in the S1 is at least one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, lactic acid, oxalic acid, citric acid, malic acid, succinic acid and tartaric acid; the silica sol in S2 is alkaline silica sol with stable ammonia; the dispersion liquid of the silicon carbide in the water is formed by the nano silicon carbide in the water through at least one process of ultrasonic treatment and stirring; in S3, the inlet temperature of a spray dryer is 180-300 ℃, and the outlet temperature is 100-150 ℃; the roasting process is to carry out denitration treatment for 1-3 hours at 200-400 ℃, and roast for 1-3 hours at 550-650 ℃.
8. Use of an attrition resistant mixed metal oxide catalyst as claimed in claim 1 or claim 3 wherein: the method is suitable for the reaction of synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon.
9. Use of an attrition resistant mixed metal oxide catalyst as claimed in claim 8 wherein: the lower hydrocarbon is at least one of propylene, propane, isobutene and isobutane; the unsaturated nitrile is at least one of acrylonitrile and methacrylonitrile.
CN202010120761.6A 2020-02-26 2020-02-26 Wear-resistant mixed metal oxide catalyst for synthesizing unsaturated nitrile by ammoxidation of low-carbon hydrocarbon and preparation method thereof Pending CN111203251A (en)

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