CN110694637A - Preparation method of supported multi-element metal oxide oxidation catalyst - Google Patents

Preparation method of supported multi-element metal oxide oxidation catalyst Download PDF

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CN110694637A
CN110694637A CN201910970834.8A CN201910970834A CN110694637A CN 110694637 A CN110694637 A CN 110694637A CN 201910970834 A CN201910970834 A CN 201910970834A CN 110694637 A CN110694637 A CN 110694637A
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catalyst
coo
oxidation catalyst
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microspheres
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邹德强
程晓霞
姜超
李祎
张云邦
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Dalian First Organic Chemical 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/40—
    • B01J35/51—
    • B01J35/615—
    • B01J35/617—
    • B01J35/618—
    • B01J35/633—
    • B01J35/635—
    • B01J35/638—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

A preparation method of a supported multi-element metal oxide oxidation catalyst belongs to the field of oxidation catalyst preparation of a michelia alcohol production process, and comprises the following steps: a. pretreating a catalyst carrier; b. preparing dipping solution, c, loading and positioning treatment, d, roasting. The catalyst is applied to the oxidation method for preparing the michelia alcohol, and the reaction speed is obviously higher than that of the traditional oxidation catalyst; the catalyst has better selectivity, and the conversion rate of reactants in unit time is greatly improved compared with that of a cobalt or manganese single-component oxidation catalyst; meanwhile, the catalyst is suitable for different reaction systems, and the reaction time can be shortened and the energy consumption can be reduced no matter the raw materials are dissolved in an acid or in an organic solvent system, so that the production cost is reduced.

Description

Preparation method of supported multi-element metal oxide oxidation catalyst
Technical Field
The invention belongs to the field of preparation of oxidation catalysts in a michelian alcohol production process, and particularly relates to a preparation method of a supported multi-element metal oxide oxidation catalyst.
Background
Tetramethyl-miglitol (4, 4' -bis-dimethylamino diphenyl carbinol) is a very important intermediate compound and can be widely applied to chemical synthesis of products such as medicines, pesticides, dyes and the like. Generally, the preparation process has two routes: firstly, preparing tetramethyl-miglitol by a methane-bis (4, 4' -bis-dimethylamino-diphenylmethane) oxidation method; the other is prepared by a reduction method of the michaelis-son (4, 4' -di (N, N-dimethylamino) benzophenone). In contrast, the oxidation process for producing mikaol is a superior process in terms of the convenience of raw material sources, the complexity of process conditions and the high and low comprehensive consideration of production cost. The heart of the oxidation process is the oxidation catalyst.
Figure DEST_PATH_IMAGE001
In the production of the oxidation process Michler's alcohol, domestic enterprises adopt a process of using 30% of hydrogen peroxide as an oxidant. The process using hydrogen peroxide is easy to explode due to improper control, and a brown oily byproduct is easily generated in the oxidation process by adopting the hydrogen peroxide, so that the yield of the product is greatly influenced.
In addition, enterprises adopt air or oxygen as an oxidant to realize oxidation reaction under the action of a catalyst. The oxidation catalyst can be cobalt acetate, cobalt oxide, lead dioxide, lead tetraacetate, sulfonated iron phthalocyanine or potassium dichromate, etc.
With the stricter environmental protection requirements, the environmental risk problem faced by the use of lead dioxide, lead tetraacetate, potassium dichromate and other catalysts is more and more severe, and these catalysts are gradually abandoned or eliminated. Therefore, research and development are urgently needed for the preparation of the oxidation catalyst to meet the application in the production of the michelia alcohol and avoid the damage to the environment caused by the traditional method.
Disclosure of Invention
The invention aims to provide a preparation method of a supported multi-element metal oxide oxidation catalyst, which solves the defects of the problems and adopts a cobalt-manganese-cerium multi-element supported oxidation catalyst to replace the traditional catalyst so as to achieve high-efficiency catalytic action.
The invention relates to a preparation method of a supported multi-element metal oxide oxidation catalyst, which is realized by the following mode and is characterized in that the preparation method comprises the following steps:
a. pretreatment of the catalyst carrier: activated gamma-Al2O3Washing microsphere with water to remove fine dust, draining, soaking in 2% dilute nitric acid or hypochlorous acid or 10% hydrogen peroxide solution for 1-5 hr, washing with water and draining, soaking in 0.1-0.5mol/L dilute HCl for 10-24 hr, washing with water, and oven drying to obtain activated γ -Al2O3Active microsphere as the carrier of catalyst. The gamma-Al2O3Microspheres of diameter 1 ~ 5mm and pore volume>0.4mL/g, specific surface area>200m2(g), bulk density of 0.5 ~ 0.7.7 Kg/L, mean value of radial crush strength>80N。
b. Preparation of the impregnation solution: configuration of Co (CH)3COO)2、Mn(CH3COO)2With CeCl3The molar ratio is (10-5): (10-5): 1, wherein said Co (CH)3COO)2Is Co (CH)3COO)2·4H2O crystal, said Mn (CH)3COO)2Is Mn (CH)3COO)2·4H2O crystal, said CeCl3Is CeCl3·7H2Adding Pt or Pb or Cu or Sn auxiliary agent into the mixed solution, and adding 1% -5% glacial acetic acid into the mixed solution.
c. And (3) loading and positioning processing: gamma-Al in the step a2O3Placing the active microsphere carrier into a dispersing agent, soaking for 1-5h, intermittently stirring, then adding the mixed solution obtained in the step b, intermittently stirring, soaking for 5-24h to obtain a pink sphere, and then placing the pink sphere into a positioning agent solution, stirring and soaking for 10-120min to obtain a precursor of the catalyst;
d. roasting: and d, drying the precursor obtained in the step c after draining, roasting the dried light blue sphere to obtain a roasted product, wherein the roasting temperature is 350-650 ℃, the roasting time is 2-5h, and washing and drying the roasted product to obtain the supported multi-element metal oxide oxidation catalyst.
The dispersant is one or more combined reagents of polyaspartic acid or polyaminoamide phosphate or polyethylene imine salt or glyceryl myristate.
The positioning agent is a mixture of NaOH or KOH and polyalcohol and hydroxyethyl cellulose and coconut diethanolamide.
The water used in steps a to d is deionized water.
The catalyst metal ions of the further preparation method do not need a reduction process and are directly oxidized by a roasting method.
The invention has the advantages of higher oxidation activity, and obviously higher reaction speed than the traditional oxidation catalyst when being applied to the preparation of the michelia alcohol by an oxidation method; the catalyst has better selectivity, and the conversion rate of reactants in unit time is greatly improved compared with that of a cobalt or manganese single-component oxidation catalyst; meanwhile, the catalyst is suitable for different reaction systems, and the reaction time can be shortened and the energy consumption can be reduced no matter the raw materials are dissolved in an acid or in an organic solvent system, so that the production cost is reduced; the catalyst also has the characteristics of simple and safe preparation process, no complex reaction process, no special requirement on a production device, strong operability, stable catalytic performance, repeated use, low cost and the like.
Drawings
FIG. 1 is a graph of a curve of a table;
FIG. 2 is a graph of a curve of the second table;
FIG. 3 is a table three-curve graph;
FIG. 4 is a graph of a table of four curves;
FIG. 5 is a graph of a table of five curves;
FIG. 6 is a graph of the table hexagram.
Detailed Description
A preparation method of a supported multi-element metal oxide oxidation catalyst comprises the following steps:
a. pretreatment of the catalyst carrier: activated gamma-Al2O3Washing microsphere with water to remove fine dust, draining, soaking in 2% dilute nitric acid or hypochlorous acid or 10% hydrogen peroxide solution for 1-5 hr, washing with water and draining, soaking in 0.1-0.5mol/L dilute HCl for 10-24 hr, washing with water, and oven drying to obtain activated γ -Al2O3Active microspheres which are used as a carrier of the catalyst;
b. preparation of the impregnation solution: configuration of Co (CH)3COO)2、Mn(CH3COO)2With CeCl3The molar ratio is (10-5): (10-5): 1, wherein said Co (CH)3COO)2Is Co (CH)3COO)2·4H2O crystal, said Mn (CH)3COO)2Is Mn (CH)3COO)2·4H2O crystal, said CeCl3Is CeCl3·7H2O crystal, adding Pt or Pb or Cu or Sn auxiliary agent into the mixed solution;
c. and (3) loading and positioning processing: gamma-Al in the step a2O3Placing the active microsphere carrier into a dispersing agent, soaking for 1-5h, intermittently stirring, then adding the mixed solution obtained in the step b, intermittently stirring, soaking for 5-24h to obtain a pink sphere, and then placing the pink sphere into a positioning agent solution, stirring and soaking for 10-120min to obtain a precursor of the catalyst;
d. roasting: and d, drying the precursor obtained in the step c after draining, roasting the dried light blue sphere to obtain a roasted product, washing and drying the roasted product to obtain the supported multi-element metal oxide oxidation catalyst.
The gamma-Al2O3Microspheres of diameter 1 ~ 5mm and pore volume>0.4mL/g, specific surface area>200m2(g), bulk density of 0.5 ~ 0.7.7 Kg/L, mean value of radial crush strength>80N。
The dispersant is one or more combined reagents of polyaspartic acid or polyaminoamide phosphate or polyethylene imine salt or glyceryl myristate.
The positioning agent is a mixture of NaOH or KOH and polyalcohol and hydroxyethyl cellulose and coconut diethanolamide.
And b, adding 1-5% of glacial acetic acid into the mixed solution in the step b.
The roasting temperature in the step d is 350-650 ℃, and the roasting time is 2-5 h.
The water in the step a and the step d is deionized water.
Example 1
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.320 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, then mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and diluting the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 2
Weighing Co (CH)3COO)2·4H22.120g of O crystal is placed in a 500mL beaker, 1.0mL of glacial acetic acid is added, water is added for dissolution and dilution to 100mL, and 100 g of activated gamma-Al is slowly added into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 3
Weighing Mn (CH)3COO)2·4H22.080g of O crystal, placing in a 500mL beaker, adding 1.0mL of glacial acetic acid, adding water to dissolve and dilute to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and collectinggamma-Al is extracted2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 4
Weighing CeCl3·7H20.320 g of O crystal is placed in a 500mL beaker, 1.0mL of glacial acetic acid is added, water is added for dissolution and dilution to 100mL, and 100 g of activated gamma-Al is slowly added into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 5
Preparing the multicomponent oxide catalyst with Co content of 0.1%, weighing Co (CH)3COO)2·4H2O crystal 0.430g, Mn (CH)3COO)2·4H2O crystals 0.420g, CeCl3·7H20.070 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, mixing the three, placing the mixture into a 500mL beaker, adding 1.0mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and dilute the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 6
Preparing the multicomponent oxide catalyst with Co content of 0.3%, weighing Co (CH)3COO)2·4H2O crystal 1.270g, Mn (CH)3COO)2·4H2O crystal 1.250g, CeCl3·7H20.200 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and dilute the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3Drying the microspheres at 105 ~ 110 deg.C and baking at 450 deg.C in muffle furnaceAnd (4) burning for 4 hours to obtain the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 7
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.400 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 8:8:1, then mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and diluting the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 8
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.640 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 5:5:1, then mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and diluting the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 9
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.320 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, then mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and diluting the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 350 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 10
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.320 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, then mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and diluting the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 550 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 11
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.320 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, then mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and diluting the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 650 ℃ for 4 hours to obtain the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 12
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.320 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, mixing the three, and placing the mixture in a 500mL beakerAdding 1.5mL of glacial acetic acid, adding water to dissolve and dilute to 100mL, and slowly adding 100 g of activated gamma-Al into a beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 2h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 13
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.320 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, then mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and diluting the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 3h to obtain the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 14
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 2.120g, Mn (CH)3COO)2·4H2O crystals 2.080g, CeCl3·7H20.320 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, then mixing the three, placing the mixture into a 500mL beaker, adding 1.5mL of glacial acetic acid, adding water to dissolve the glacial acetic acid and diluting the glacial acetic acid to 100mL, and slowly adding 100 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 5 hours to obtain the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Example 15
Preparing the multicomponent oxide catalyst with Co content of 0.5%, weighing Co (CH)3COO)2·4H2O crystal 21.15g, Mn (CH)3COO)2·4H2O crystal20.80g of cerium oxide, CeCl3·7H23.18 g of O crystal, wherein the molar ratio of cobalt, manganese and cerium is 10:10:1, then mixing the three, placing the mixture into a 5000mL beaker, adding 15mL of glacial acetic acid, adding water to dissolve and dilute the glacial acetic acid to 1000mL, and slowly adding 1000 g of activated gamma-Al into the beaker2O3Soaking the microspheres overnight, and taking out the gamma-Al2O3And (3) drying the microspheres at 105 ~ 110 ℃ and roasting the microspheres in a muffle furnace at 450 ℃ for 4h to prepare the cobalt-manganese-cerium multi-element supported oxidation catalyst.
Analysis of oxidation reaction experiment results:
in order to examine the oxidation performance of different metal oxide catalysts, the catalysts prepared in different examples were respectively reacted under the same experimental conditions, and the conversion rates were measured and the experimental results were compared.
Experimental scheme for preparing tetramethylMil alcohol by methane Bessel oxidation reaction:
weighing about 5.0g of methane bass, dissolving in 60ml of hot ethanol, adding an oxidation catalyst, introducing air for oxygen supply by a bubbling method, reacting at normal pressure, wherein the amount of the air is 1.0L/min, the reaction time is 30min ~ 120min, and the reaction temperature is 62 ℃ ~ 90 ℃.
A first table: comparing the blank group with the single-component and multi-component supported oxide catalyst;
30min 60min 90min 120min
γ-Al2O3 3.5% 5.2% 7.3% 10.1%
Co/γ-Al2O3 23.3% 53.7% 79.8% 89.7%
Mn/γ-Al2O3 19.5% 42.1% 59.3% 71.8%
Ce/γ-Al2O3 11.9% 25.4% 47.8% 59.7%
example 1 31.7% 72.5% 90.2% 94.6%
Example 15 31.2% 73.1% 90.4% 94.2%
Table two: metal Co loading: 1 per mill, 0.3 percent and 0.5 percent;
30min 60min 90min 120min
example 5 (0.1%) 9.9% 26.7% 53.5% 71.2%
Example 6 (0.3%) 23.3% 53.7% 69.8% 85.6%
Example 1 (0.5%) 31.7% 72.5% 90.2% 94.6%
Table three: 0.5% metal molar ratio: 10:10:1, 8:8, 1, 5:5: 1;
30min 60min 90min 120min
example 1 (10: 10: 1) 31.7% 72.5% 90.2% 94.6%
Example 7 (8: 8: 1) 39.4% 77.1% 92.5% 95.2%
Example 8 (5: 5: 1) 43.7% 85.2% 94.9% 95.7%
Table four: the roasting temperature is 4 h: 350 ℃, 450 ℃, 550 ℃ and 650 DEG C
30min 60min 90min 120min
Example 9 (350 ℃ C.) 30.2% 74.3% 86.7% 93.1%
Example 1 (450 ℃ C.) 31.7% 72.5% 90.2% 94.6%
Example 10 (550 ℃ C.) 31.1% 73.3% 91.8% 94.1%
Example 11 (650 ℃ C.) 28.7% 66.9% 85.1% 90.6%
Table five: roasting time is 450 ℃: 2h, 3h, 4h and 5h
30min 60min 90min 120min
Example 12 (2 h) 28.6% 68.8% 83.1% 88.6%
Example 13 (3 h) 30.7% 71.7% 87.6% 93.5%
Example 1 (4 h) 31.7% 72.5% 90.2% 94.6%
Example 14 (5 h) 27.9% 70.6% 86.7% 92.9%
Table six: the application times are as follows: 1, 2, 3, 4, 5 (example 1)
Example 1 30min 60min 90min 120min
1 st time 31.7% 72.5% 90.2% 94.6%
2 nd time 32.5% 71.9% 89.4% 93.9%
3 rd time 30.8% 72.1% 91.1% 94.0%
4 th time 29.7% 70.2% 88.9% 94.1%
5 th time 28.2% 68.7% 87.2% 94.3%

Claims (7)

1. A preparation method of a supported multi-element metal oxide oxidation catalyst is characterized by comprising the following steps:
a. pretreatment of the catalyst carrier: activated gamma-Al2O3Washing microsphere with water to remove fine dust, draining, soaking in 2% dilute nitric acid or hypochlorous acid or 10% hydrogen peroxide solution for 1-5 hr, washing with water and draining, soaking in 0.1-0.5mol/L dilute HCl for 10-24 hr, washing with water, and oven drying to obtain activated γ -Al2O3Active microspheres which are used as a carrier of the catalyst;
b. preparation of the impregnation solution: configuration of Co (CH)3COO)2、Mn(CH3COO)2With CeCl3The molar ratio is (10-5): (10-5): 1, wherein said Co (CH)3COO)2Is Co (CH)3COO)2·4H2O crystal, said Mn (CH)3COO)2Is Mn (CH)3COO)2·4H2O crystal, said CeCl3Is CeCl3·7H2O crystal, adding Pt or Pb or Cu or Sn auxiliary agent into the mixed solution;
c. and (3) loading and positioning processing: gamma-Al in the step a2O3Placing the active microsphere carrier into a dispersing agent, soaking for 1-5h, intermittently stirring, then adding the mixed solution obtained in the step b, intermittently stirring, soaking for 5-24h to obtain a pink sphere, and then placing the pink sphere into a positioning agent solution, stirring and soaking for 10-120min to obtain a precursor of the catalyst;
d. roasting: and d, drying the precursor obtained in the step c after draining, roasting the dried light blue sphere to obtain a roasted product, washing and drying the roasted product to obtain the supported multi-element metal oxide oxidation catalyst.
2. The method of claim 1, wherein the γ -Al is selected from the group consisting of2O3Microspheres of diameter 1 ~ 5mm and pore volume>0.4mL/g, specific surface area>200m2(g), bulk density of 0.5 ~ 0.7.7 Kg/L, mean value of radial crush strength>80N。
3. The method of claim 1, wherein the dispersant is one or more of polyaspartic acid, polyaminoamide phosphate, polyethyleneimine salt, and glyceryl myristate.
4. The method of claim 1, wherein the positioning agent is a mixture of NaOH or KOH and a polyol, hydroxyethyl cellulose, or coconut diethanolamide.
5. The method of claim 1, wherein 1% -5% glacial acetic acid is added to the mixed solution in step b.
6. The method of claim 1, wherein the calcination temperature in step d is 350-650 ℃ and the calcination time is 2-5 h.
7. The method of claim 1, wherein the water used in steps a and d is deionized water.
CN201910970834.8A 2019-10-14 2019-10-14 Preparation method of supported multi-element metal oxide oxidation catalyst Pending CN110694637A (en)

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