CN111151265A - Supported honeycomb catalyst, preparation method and application thereof - Google Patents

Supported honeycomb catalyst, preparation method and application thereof Download PDF

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CN111151265A
CN111151265A CN201811325560.9A CN201811325560A CN111151265A CN 111151265 A CN111151265 A CN 111151265A CN 201811325560 A CN201811325560 A CN 201811325560A CN 111151265 A CN111151265 A CN 111151265A
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catalyst
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active metal
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王胜
徐德康
王树东
汪明哲
林乐
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Dalian Institute of Chemical Physics of CAS
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
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    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/0215—Coating

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Abstract

The application discloses a supported honeycomb catalyst, a preparation method thereof and application thereof in the treatment of waste gas containing acrylonitrile. The catalyst comprises a catalytic coating and a honeycomb carrier; the catalytic coating comprises an active component and a mesoporous metal oxide carrier; the active component comprises an active metal element, and the active metal element is selected from at least one of Cu, Ag and Ce. The catalyst has high catalytic activity and selectivity, simple preparation process, low cost of raw materials, basically no by-products, low energy consumption and wide industrial application value.

Description

Supported honeycomb catalyst, preparation method and application thereof
Technical Field
The application relates to a high-selectivity high-hydrothermal-stability acrylonitrile waste gas purification catalyst and a preparation method thereof, belonging to the field of acrylonitrile waste gas purification.
Background
Acrylonitrile is an important chemical intermediate, an intermediate monomer for synthetic fibers, synthetic rubbers and synthetic resins, and has a very wide range of applications.
At present, acrylonitrile is mainly produced by ammoxidation of propylene. The waste Gas discharged from the top of the absorption tower in the propylene ammoxidation process is called absorption tower tail Gas (AOG), which is one of the main pollution sources in the petrochemical industry, and comprises non-methane hydrocarbons, carbon monoxide, carbon dioxide, nitrogen oxides, cyanide-containing substances (acrylonitrile, hydrocyanic acid, acetonitrile) and the like besides the main component of nitrogen. According to the latest discharge Standard of pollutants for petrochemical industry (GB 31571-2015) in China, the acrylonitrile content in the discharged waste gas is lower than 0.5mg/m3Hydrogen cyanide is less than 1.9mg/m3Therefore, the tail gas of the absorption tower is directly discharged into the atmosphere, which causes serious environmental pollution.
There are two different methods for industrially treating acrylonitrile tail gas by catalytic combustion, namely, a noble metal catalyst combined selective catalytic reduction catalyst and a Cu-ZSM-5 molecular sieve-based catalyst. Patents CN101269297A and CN1404900A disclose a precious metal catalyst of platinum, palladium and rhodium for removing HCN waste gas, which has high cost of precious metals and poor selectivity. Patent CN201310111636.9 discloses a Cu/ZSM-5 acrylonitrile tail gas purification catalyst, although the catalyst has a high N2Selectivity; however, the catalyst has poor hydrothermal stability and is difficult to satisfy industrial application requirements. Patent CN146252A discloses Al for removing HCN waste gas2O3The Cu-loaded catalyst is used, and the reaction temperature for removing gas is 150-300 ℃. The reaction temperature required by the purification of acrylonitrile tail gas is as high as 650 ℃, and the catalyst disclosed in the patent 1462652A is difficult to meet the requirement of acrylonitrileThe requirement of tail gas purification working conditions.
Disclosure of Invention
According to one aspect of the application, the supported honeycomb catalyst has high catalytic activity and selectivity, the preparation process of the catalyst is simple, the raw material price is low, byproducts are not generated basically, the energy consumption is low, and the supported honeycomb catalyst has wide industrial application value.
The supported honeycomb catalyst is characterized by comprising a catalytic coating and a honeycomb carrier;
the catalytic coating comprises an active component and a mesoporous metal oxide carrier;
the active component comprises an active metal element, and the active metal element is selected from at least one of Cu, Ag and Ce.
Optionally, the active metal element includes Cu, Ag.
Optionally, the active metal element is selected from Cu, Ag, Ce.
Optionally, the weight percentage of the active component in the catalytic coating is 0.1% to 25%.
Optionally, the weight percentage of the active component in the catalytic coating is 4% to 20%.
Optionally, the weight percentage of the active component in the catalytic coating is 4.1-25%;
the weight percentage of the active component is calculated by the weight percentage of the active metal element.
Optionally, the active metal elements include Cu and Ag; the molar ratio of the Cu to the Ag is 4-1: 1.
Optionally, the active metal elements are Cu, Ag and Ce; the weight percentage content of the Cu in the catalytic coating is 3-10%;
the weight percentage of the Ag in the catalytic coating is 1-10%;
the weight percentage of the Ce in the catalytic coating is 0.1-5%.
Optionally, the weight percentage ratio of Cu, Ag, and Ce is 4:2:1 or 4:2: 2.
optionally, the weight percentage ratio of the Cu, Ag, Ce and the mesoporous metal oxide support is 4:2:1: 100.
optionally, the mesoporous metal oxide is selected from mesoporous gamma-Al2O3。
Alternatively, the gamma-Al2O3The pore size distribution of (A) is 2nm to 10 nm.
Optionally, the honeycomb carrier is cordierite.
As an implementation mode, aiming at the removal process of acrylonitrile waste gas, CuAgCe/gamma-Al is provided2O3The catalyst and the method for catalyzing and burning the acrylonitrile waste gas can efficiently remove the acrylonitrile waste gas in a wider temperature range (300-600 ℃). Aiming at the highly toxic gas of acrylonitrile discharged by an acrylonitrile plant, the catalyst has high catalytic activity and selectivity, simple preparation process, low raw material price, basically no by-product, low energy consumption and wide industrial application value.
As an embodiment, the application provides a high-selectivity high-hydrothermal-stability acrylonitrile exhaust gas purification catalyst, wherein the catalyst is a supported honeycomb catalyst, and the structural form of the supported honeycomb catalyst is CuxAgyCe1-x-y/Al2O3A honeycomb carrier.
Alternatively, Al2O3Is mesoporous gamma-Al2O3The weight of Cu accounts for 3-10% of the total weight of the catalyst coating; the weight of Ag accounts for 1-10% of the total weight of the catalyst coating; the weight of Ce accounts for 0.1-5% of the total weight of the catalyst coating. The mass of the support and the metal affect the number of active centers of the catalyst, Cu: ag: ce: gamma-Al2O3The ratio is preferably 4:2:1: 100.
According to another aspect of the present application, a method of preparing a supported honeycomb catalyst is provided.
The preparation method of the supported honeycomb catalyst is characterized by comprising the following steps of:
(1) immersing the mesoporous metal oxide in a solution containing an active metal element precursor, drying, and roasting I to obtain a precursor I loaded with an active component;
(2) and (3) soaking the honeycomb carrier in the slurry containing the precursor I, drying, and roasting II to obtain the supported honeycomb catalyst.
Optionally, the drying temperature in the step (1) is 100-200 ℃, and the drying time is 4-48 hours.
Optionally, the conditions of the roasting I in the step (1) are as follows: roasting at 300-700 ℃ for 2-8 hours.
Alternatively, the upper limit of the temperature of the calcination I in (1) is selected from 400 ℃, 500 ℃, 600 ℃, or 700 ℃; the lower limit is selected from 300 deg.C, 400 deg.C, 500 deg.C or 600 deg.C.
Alternatively, the upper limit of the time of the calcination I in (1) is selected from 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours; the lower limit is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or 7 hours.
Alternatively, the upper limit of the temperature of the drying in (1) is selected from 120 ℃, 150 ℃, 180 ℃ or 200 ℃; the lower limit is selected from 100 deg.C, 120 deg.C, 150 deg.C or 180 deg.C.
Optionally, step (1) comprises:
a1) immersing the mesoporous metal oxide in a solution containing an active component precursor, and roasting for 2-8 hours at 300-700 ℃ to obtain a sample I; the impregnation is equal-volume impregnation; the impregnation conditions are as follows: drying for 4-48 hours at 100-200 ℃;
a2) and ball-milling the mixed solution containing the sample I and the binder for 0.5-36 hours at the rotating speed of 300-600r/min to obtain the slurry.
Alternatively, the upper limit of the temperature of the calcination in a1) is selected from 400 ℃, 500 ℃, 600 ℃ or 700 ℃; the lower limit is selected from 300 deg.C, 400 deg.C, 500 deg.C or 600 deg.C.
Alternatively, the upper limit of the time of the calcination in a1) is selected from 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours; the lower limit is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or 7 hours.
Alternatively, the upper limit of the temperature of said drying in a1) is selected from 120 ℃, 150 ℃, 180 ℃ or 200 ℃; the lower limit is selected from 100 deg.C, 120 deg.C, 150 deg.C or 180 deg.C.
Optionally, step (1) comprises: and ball-milling the mixed solution containing the mesoporous oxide, the active component precursor salt and the binder at the rotating speed of 300-600r/min for 0.5-36 hours to obtain the slurry.
Optionally, the upper limit of the rotation speed in the step (1) is selected from 400r/min, 500r/min or 600 r/min; the lower limit is selected from 300r/min, 400r/min or 500 r/min.
Alternatively, the upper limit of the time of the ball milling in step (1) is selected from 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 25 hours, 30 hours, or 36 hours; the lower limit is selected from 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 25 hours, or 30 hours.
Optionally, the preparation method of the mesoporous metal oxide in step (1) is selected from hydrothermal synthesis, sol-gel method, soft template method, ionic liquid method, reverse microemulsion method, and hard template method.
Optionally, the mesoporous metal oxide is mesoporous gamma-Al2O3。
Optionally, the active metal element precursor in step (1) is selected from at least one of the active metal salts.
Optionally, the active metal element precursor comprises one of nitrate, acetate, sulfate, carbonate and chloride of the active metal element.
Optionally, the precursor containing the active component in step (1) includes a Cu precursor salt, a Ag precursor salt, and a Ce precursor salt.
Optionally, the precursor salt of Ag is at least one selected from silver nitrate, silver acetate and silver chloride;
the Cu precursor salt is selected from at least one of copper nitrate, copper sulfate, copper chloride and copper acetate;
the precursor salt of Ce is selected from at least one of cerium nitrate, ammonium cerium nitrate and cerium carbonate.
Alternatively, the impregnation in step (1) is an equal volume impregnation.
Optionally, step (1) is: and (3) carrying out ball milling on the raw materials containing the mesoporous oxide and the active metal element precursor to obtain the slurry containing the precursor I.
Optionally, step (1) is: and carrying out ball milling on the raw materials containing the mesoporous oxide, the active metal element precursor and the binder to obtain the slurry containing the precursor I.
Optionally, the drying temperature in the step (2) is 120-200 ℃, and the drying time is 4-48 hours.
Optionally, the conditions for the roasting II in the step (2) are as follows: roasting at 300-700 ℃ for 1-6 hours.
Optionally, the upper limit of the temperature of the firing II in (2) is selected from 400 ℃, 500 ℃, 600 ℃, or 700 ℃; the lower limit is selected from 300 deg.C, 400 deg.C, 500 deg.C or 600 deg.C.
Alternatively, the upper limit of the time for the calcination in (2) is selected from 3 hours, 4 hours, 5 hours, or 6 hours; the lower limit is selected from 1 hour, 2 hours, 3 hours, 4 hours or 5 hours.
Alternatively, the upper limit of the temperature of said drying in a1) is selected from 120 ℃, 150 ℃, 180 ℃ or 200 ℃; the lower limit is selected from 100 deg.C, 120 deg.C, 150 deg.C or 180 deg.C.
Optionally, the solid-to-liquid ratio of the impregnation in the step (2) is 1-2: 1-10.
Optionally, the slurry in the step (2) contains a binder.
Optionally, the binder in step (2) is selected from at least one of pseudo-boehmite and alumina sol.
The slurry in the step (2) is obtained by ball milling of a raw material containing a precursor I, wherein the ball milling conditions are as follows: ball milling is carried out for 0.5-36 hours at the rotating speed of 300-600 r/min.
Optionally, in the step (2), the honeycomb carrier is immersed in the slurry for 1-4 minutes, and is subjected to purging, drying at 120-200 ℃ for 4-48 hours, and roasting at 300-700 ℃ for 1-6 hours to obtain the supported honeycomb catalyst.
As an embodiment, a high selectivity and high hydrothermal stability acrylonitrile waste gas purification catalyst is prepared by the following method:
1) firstly, the mesoporous gamma-Al with narrow pore distribution is synthesized by a hydrothermal synthesis method, a sol-gel method, a soft template method, an ionic liquid method, a reverse microemulsion method, a hard template method and the like2O3；γ-Al2O3The pore size distribution of the porous material is about 2nm to 10 nm;
2) mixing Cu: ag: ce: gamma-Al2O3Preparing a precursor salt solution of Cu, Ag and Ce with a certain concentration, and soaking the precursor salt solution in the prepared gamma-Al in equal volume2O3Drying the carrier on a carrier at 100-200 ℃ overnight, and roasting the carrier for 2-8 hours at 300-700 ℃ to obtain M/gamma-Al loaded with active components2O3Powder; roasting at the preferred roasting temperature of 400-700 ℃ for 4-6 hours;
3) a certain amount of M/gamma-Al is added2O3Powder (0-90%), pseudo-boehmite (0-10%), alumina sol (0-20%) and water, and preparing slurry by high-energy ball milling for 0.5-36 hours, preferably 2-4 hours in a ball mill at the rotating speed of 300-;
4) dipping the ceramic honeycomb carrier in the slurry prepared in the step 3) for 1-4min, and then blowing off the redundant slurry by using compressed air; then, drying at 120-200 ℃, and roasting at 300-700 ℃ for 1-6 hours, preferably at 450-700 ℃ for 2-4 hours to obtain the catalyst.
The preparation steps 2) and 3) can also be carried out by mixing gamma-Al2O3(0-90%), pseudo-boehmite (0-10%), alumina sol (0-20%), Cu, Ag, Ce precursor salt solution with certain concentration, water and the like, and preparing slurry by high-energy ball milling for 0.5-36 hours, preferably 2-4 hours in a ball mill at the rotating speed of 300-600r/min, preferably 400-500 r/min;
in the preparation process of the catalyst for purifying acrylonitrile waste gas with high selectivity and high hydrothermal stability, Cu precursor salts are copper nitrate, copper sulfate, copper chloride and copper acetate; precursor salts of Ag are silver nitrate, silver acetate and silver chloride; the precursor salt of Ce is cerous nitrate, ammonium ceric nitrate and cerous carbonate.
According to still another aspect of the present application, there is provided an acrylonitrile exhaust gas purification catalyst, characterized by comprising at least one of the supported honeycomb catalyst and the supported honeycomb catalyst prepared according to the method.
According to still another aspect of the present application, there is provided an acrylonitrile exhaust gas purification method characterized by reacting acrylonitrile exhaust gas in the presence of a catalyst;
the catalyst is at least one selected from the supported honeycomb catalyst, the supported honeycomb catalyst prepared by the method and the acrylonitrile exhaust gas purification catalyst.
Optionally, the reaction conditions are: the reaction temperature is 300-700 ℃, and the gas volume space velocity is 10,000-50,000 h-1。
Optionally, introducing waste gas containing acrylonitrile into a reactor containing the catalyst to perform reaction; the reaction temperature is 300-700 ℃; the gas airspeed of the waste gas containing acrylonitrile is 10000-50000 h-1。
Putting a catalyst sample in a fixed bed quartz tube reactor, and putting a mixed gas of acrylonitrile, nitric oxide, carbon monoxide, propylene, propane, oxygen, water vapor and nitrogen at a volume space velocity of 10,000h at normal pressure and within the range of 200-700 DEG C-1～50,000h-1And (3) introducing the waste gas into a reactor, and removing the waste gas through catalytic combustion, wherein the volume of the mixed gas consists of acrylonitrile: nitric oxide: carbon monoxide: propylene: propane: oxygen: the steam is 0.22:0.06:0.54:0.09:0.09: 1-5: 3.5, and nitrogen is used as balance gas.
In the gas removal process, the volume ratio of the concentration of acrylonitrile to the concentration of oxygen is preferably 0.22:1 according to the acrylonitrile tail gas treatment conditions.
In the application, "acrylonitrile waste gas" refers to the practical industrial working condition applicable to the catalyst, and industrially, the tail gas of the acrylonitrile absorption tower contains about 3,000ppm of non-methane hydrocarbons, about 8,000ppm of carbon monoxide, about 400ppm of nitrogen oxides and a small amount of acrylonitrile.
The beneficial effects that this application can produce include:
1) the catalyst provided by the application adopts mesoporous Al2O3The catalyst is a carrier, so that the catalyst has high specific surface area and high hydrothermal stability, and the practicability of the catalyst in the acrylonitrile tail gas purification process is improved;
2) the catalyst provided by the application adopts transition metal, rare earth elements and Ag which is relatively cheap, reduces the cost of the catalyst, realizes low ignition temperature (300 ℃) of acrylonitrile waste gas (acrylonitrile, nitric oxide, carbon monoxide, propylene and propane), high conversion rate (100% at 320 ℃), and N2And CO2The selectivity is high;
3) the catalyst provided by the application designs a simple and reasonable method, active components are uniformly impregnated on a carrier, and the integral structured catalyst is prepared by adopting a coating method, so that the high dispersion of active centers and high-efficiency catalytic activity and selectivity are ensured.
Drawings
FIG. 1 shows that different loading amounts of copper-silver catalyst are used for catalyzing and combusting N in acrylonitrile waste gas2Yield as a function of temperature.
FIG. 2 shows the N content in acrylonitrile waste gas catalytic combustion of cerium catalysts with the same loading amount, copper and silver and different loading amounts2Yield as a function of temperature.
FIG. 3 is a 100h stability evaluation of a cerium catalyst loaded with 4% Cu, 2% Ag and 1%, where the space velocity is 40,000h-1；
FIG. 4 depicts acrylonitrile and acrylonitrile C of example 13H6、C3H8CO conversion and N2The yield of (a).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
In the examples, the conversion calculation formula is:
Figure BDA0001858653220000081
in the formula: cinIs the inlet gas component concentration; coutIs the outlet gas component concentration.
Example 1:
firstly, preparing mesoporous gamma-Al with narrow pore distribution by a hydrothermal synthesis method (a conventional hydrothermal synthesis method belongs to the prior art)2O3Weighing 9.6648g Cu (NO)3·3H2O (chemical pure reagent), 1.6987g AgNO3Dissolving (chemical pure reagent) in 98g of water to prepare a steeping liquor, wherein the molar ratio of Cu to Ag is 4:1, and weighing gamma-Al2O36.2g of the solution is put into the impregnation liquid, fully stirred, dried for 12 hours at the temperature of 120 ℃, roasted for 4 hours at the temperature of 600 ℃ to obtain M/gamma-Al2O3An active component. The mixture, 3.0g of pseudo-boehmite and 1.0g of alumina sol are put into a ball milling tank, 30g of water is added, and ball milling is carried out for 3 hours at the rotating speed of 500r/min, thus obtaining the slurry. And (3) putting 1mL of cordierite carrier into the slurry, soaking for 3min, taking out, draining, drying at 200 ℃ overnight, roasting at 650 ℃ for 4h to obtain the catalyst, and cooling to obtain the required honeycomb ceramic catalyst with the monolithic structure.
Catalyst evaluation conditions:
placing a catalyst sample in a fixed bed quartz tube reactor, and introducing a mixed gas of acrylonitrile, nitric oxide, carbon monoxide, propylene, propane, oxygen, water vapor and nitrogen at a volume space velocity of 40,000h under normal pressure-1And (3) introducing into a reaction furnace, wherein the volume composition of the mixed gas is acrylonitrile: nitric oxide: carbon monoxide: propylene: propane: oxygen: water vapor 0.22:0.06:0.54:0.09:0.09:5:3.5, nitrogen as the balance gas. Chromatographic detection of acrylonitrile and C at normal temperature3H6、C3H8After the readings are stable, the temperature starts to rise, and the temperature is detected for three times at intervals of 50 ℃ later, wherein the reaction temperature range is as follows: 200-500 ℃. Wherein the nitrogen-containing compounds in the acrylonitrile product are analyzed and monitored on line by a German Yikang Ecom & J2KN flue gas analyzer. Acrylonitrile, C3H6、C3H8CO conversion and N2The yield of (A) is shown in FIG. 4. FIG. 1 shows different negativesN in acrylonitrile waste gas catalytic combustion by loaded copper-silver catalyst2Yield as a function of temperature.
In fig. 1, it is shown that 4% by mass of copper and 2% by mass of silver are the optimum active component amounts for the catalyst coating, indicating that there is an optimum ratio of copper to silver on the support. By adjusting the content of copper and silver, the N can be obviously improved2The yield of the catalyst is improved, and the catalytic performance of the catalyst is improved.
Examples 2 to 6
The catalysts used were varied in Cu and Ag loading, from example 2 to example 6 in Cu to Ag molar ratios of 4:2, 4:3, 4:4, 5:2 and 3:3, respectively, and the other conditions were the same as in example 1. Examples 2 to 6 the catalyst evaluation procedure was the same as in example 1, and the evaluation results are shown in fig. 1.
Example 7:
firstly, synthesizing mesoporous gamma-Al with narrow pore distribution by a sol-gel method (prepared according to the method in the patent CN 104399470A)2O39.6648g of Cu (NO)3)3·3H2O (chemical pure reagent), 1.6987g AgNO3(chemical purity reagent) 4.3412gCe (NO)3)3·6H2O (chemical pure reagent), 6.2g of gamma-Al2O33.0g of pseudo-boehmite, 1.0g of alumina sol and 30g of water were put into a ball mill together, wherein the mass percentage of Cu, Ag and Ce was 4:2:1, and the preparation conditions and evaluation conditions of the remaining catalysts were the same as those of example 1. The evaluation results are shown in FIG. 2, in which FIG. 2 shows N after adding 1% by mass of cerium as a catalyst coating2The selectivity of (A) is greatly improved at a lower temperature (300 ℃), which shows that cerium can lower the temperature when acrylonitrile is completely converted.
Example 8
The mass percentage of Cu, Ag and Ce used as catalysts is 4:2:2, and the preparation conditions and evaluation conditions of the rest of the catalysts are the same as those in example 1.
Example 9:
the catalyst prepared in example 7 was evaluated for stability for 100 hours at a catalyst inlet temperature of 320 ℃ under the same evaluation conditions as in example 1. The stability evaluation is shown in FIG. 3, which shows propylene in 100h in FIG. 3The conversion rate of nitrile is above 99.5%, the conversion rate of carbon monoxide is above 80%, and N2The selectivity of the catalyst is over 78 percent, the conversion rate of propylene and propane is over 35 percent, and the catalyst can effectively convert acrylonitrile and nitric oxide into N2And has very great application prospect.
Example 10 to example 15:
example 10: the procedure is as in example 1, except that γ -Al2O3Stirring with the maceration extract, drying at 100 deg.C for 12 hr, and calcining at 300 deg.C for 8 hr;
example 11: the procedure is as in example 1, except that γ -Al2O3Stirring with the maceration extract, drying at 200 deg.C for 12 hr, and calcining at 700 deg.C for 2 hr;
example 12: the procedure is as in example 1, except that M/gamma-Al2O3Putting the active component, 3.0g of pseudo-boehmite and 1.0g of alumina sol into a ball milling tank, and ball milling for 36 hours in 30g of water at the rotating speed of 300r/min to prepare slurry;
example 13: the procedure is as in example 1, except that M/gamma-Al2O3Putting the active component, 3.0g of pseudo-boehmite and 1.0g of alumina sol into a ball milling tank, and ball milling for 0.5h at the rotating speed of 600r/min by 30g of water to prepare slurry;
example 14: the specific operation is the same as that in example 7, except that the impregnation time of the honeycomb ceramic and the slurry is 1 minute, the honeycomb ceramic and the slurry are subjected to air purging, dried at 120 ℃ for 12 hours, and calcined at 300 ℃ for 8 hours to obtain a catalyst;
example 15: the specific operation is the same as that in example 7, except that the impregnation time of the honeycomb ceramic and the slurry is 4 minutes, the honeycomb ceramic and the slurry are subjected to air purging, dried at 200 ℃ for 12 hours, and calcined at 700 ℃ for 2 hours to obtain a catalyst;
the evaluation results of the catalysts prepared in examples 10 to 15 are similar to those of fig. 1 and 2.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A supported honeycomb catalyst, characterized in that the catalyst comprises a catalytic coating and a honeycomb carrier;
the catalytic coating comprises an active component and a mesoporous metal oxide carrier;
the active component comprises an active metal element, and the active metal element is selected from at least one of Cu, Ag and Ce.
2. The catalyst according to claim 1, wherein the weight percentage of the active component in the catalytic coating is 0.1-25%;
preferably, the weight percentage content of the active component in the catalytic coating is 4-20%;
preferably, the weight percentage content of the active component in the catalytic coating is 4.1-25%;
the weight percentage of the active component is calculated by the weight percentage of the active metal element.
3. The catalyst of claim 1, wherein the active metal elements include Cu and Ag; the molar ratio of the Cu to the Ag is 4-1: 1;
preferably, the active metal elements are Cu, Ag and Ce; the weight percentage content of the Cu in the catalytic coating is 3-10%;
the weight percentage of the Ag in the catalytic coating is 1-10%;
the weight percentage content of the Ce in the catalytic coating is 0.1-5%;
further preferably, the weight percentage content ratio of the Cu, the Ag and the Ce is 4:2:1 or 4:2: 2;
still more preferably, the weight percentage ratio of the Cu, Ag, Ce and the mesoporous metal oxide support is 4:2:1: 100.
4. the catalyst of claim 1, wherein the mesoporous metal oxide is selected from mesoporous γ -Al2O3；
Preferably, the gamma-Al2O3The pore size distribution of (A) is 2nm to 10 nm.
5. The method of preparing a supported honeycomb catalyst according to claims 1 to 4, characterized by comprising the steps of:
(1) immersing the mesoporous metal oxide in a solution containing an active metal element precursor, drying, and roasting I to obtain a precursor I loaded with an active component;
(2) and (3) soaking the honeycomb carrier in the slurry containing the precursor I, drying, and roasting II to obtain the supported honeycomb catalyst.
6. The method according to claim 5, wherein the active metal element precursor in step (1) is selected from at least one of the active metal salts;
preferably, the active metal element precursor comprises one of nitrate, acetate, sulfate, carbonate and chloride of the active metal element;
preferably, the impregnation in step (1) is an equal volume impregnation.
7. The method of claim 5, wherein step (1) is: and (3) carrying out ball milling on the raw materials containing the mesoporous metal oxide and the precursor containing the active metal element to obtain the slurry containing the precursor I.
8. The method according to claim 5, wherein the solid-to-liquid ratio of the impregnation in the step (2) is 1-2: 1-10;
preferably, the slurry in the step (2) contains a binder;
preferably, the slurry in step (2) is obtained by ball milling from a raw material containing the precursor I, wherein the ball milling conditions are as follows: ball milling is carried out for 0.5-36 hours at the rotating speed of 300-600 r/min.
9. An acrylonitrile exhaust gas purification catalyst, comprising at least one of the supported honeycomb catalyst according to any one of claims 1 to 4 and the supported honeycomb catalyst produced by the method according to any one of claims 5 to 8.
10. A method for purifying acrylonitrile waste gas is characterized in that acrylonitrile waste gas is reacted in the presence of a catalyst;
the catalyst is selected from at least one of the supported honeycomb catalyst of any one of claims 1 to 4, the supported honeycomb catalyst produced by the method of any one of claims 5 to 8, the acrylonitrile exhaust gas purification catalyst of claim 9;
preferably, the reaction conditions are: the reaction temperature is 300-700 ℃, and the gas volume space velocity is 10,000-50,000 h-1。
CN201811325560.9A 2018-11-08 2018-11-08 Supported honeycomb catalyst, preparation method and application thereof Pending CN111151265A (en)

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Application publication date: 20200515