CN111111656B - High-temperature-resistant catalytic combustion catalyst capable of catalyzing and igniting VOCs (volatile organic compounds) to perform self-sustaining combustion at normal temperature and preparation method and application thereof - Google Patents
High-temperature-resistant catalytic combustion catalyst capable of catalyzing and igniting VOCs (volatile organic compounds) to perform self-sustaining combustion at normal temperature and preparation method and application thereof Download PDFInfo
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- CN111111656B CN111111656B CN201811277749.5A CN201811277749A CN111111656B CN 111111656 B CN111111656 B CN 111111656B CN 201811277749 A CN201811277749 A CN 201811277749A CN 111111656 B CN111111656 B CN 111111656B
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
Abstract
The invention relates to a high-temperature-resistant catalytic combustion catalyst for self-sustaining combustion of VOCs under normal temperature catalytic ignition, and a preparation method and application thereof. The high-temperature-resistant catalytic combustion catalyst for catalyzing and igniting VOCs at normal temperature to perform self-sustaining combustion comprises a noble metal active component, an oxygen storage material cerium-zirconium solid solution and a carrier; the carrier comprises Al 2 O 3 A carrier; wherein, based on 100 weight parts of the total weight of the catalyst, the content of noble metal active components is 0.03 to 5 weight parts, the content of cerium-zirconium solid solution of the oxygen storage material is 5 to 40 weight parts, and the balance is carrier. The catalyst of the invention can ignite VOCs material flow containing a certain amount of low unsaturated hydrocarbon and hydrogen at normal temperature (more than or equal to 30 ℃) and normal pressure, and realizes self-sustaining combustion. The catalyst can remove VOCs waste gas without external auxiliary heating energy, is quick and effective in ignition, has good hydrothermal stability and high-temperature stability, and greatly simplifies the treatment of treating the VOCs waste gas.
Description
Technical Field
The invention relates to a high-temperature-resistant catalytic combustion catalyst for self-sustaining combustion of normal-temperature catalytic ignition VOCs in the field of catalysts, in particular to a high-temperature-resistant catalytic combustion catalyst for self-sustaining combustion of normal-temperature catalytic ignition VOCs, and a preparation method and application thereof.
Background
Volatile organic compounds (Volatile Organic Compounds, VOCs for short) refer to organic compounds with saturated vapor pressure at normal temperature of more than 70Pa and boiling point at normal pressure of less than 260 ℃. Mainly comprises aromatic hydrocarbon, aliphatic hydrocarbon, halohydrocarbon, oxygenated hydrocarbon, terpene hydrocarbon, alcohol, aldehyde, ketone, ester, etc. They are the main pollutants in exhaust gases from petrochemical, pharmaceutical, printing, paint spraying and other industries. Most of the organic matters have toxicity and malodor, part of the organic matters can be cancerogenic, and most of the VOCs have a destructive effect on an ozone layer. The society pays more and more attention to the treatment of VOCs, and common VOCs purification technologies include a condensation method, an adsorption method, an absorption method, a catalysis method, a biological method and the like, and the methods are widely applied. Wherein the catalytic method is to heat the VOCs to the ignition temperature (200-400 ℃) to realize the catalytic and non-catalytic combustion reaction of the VOCs to generate carbon dioxide and water.
The existing catalysts used in the catalytic method are supported noble metal catalysts, and the supported noble metal catalysts have the advantages of low ignition temperature and high activity, but have the defects of high price, easy burning, sublimation and inactivation of active components at high temperature, poor stability, low poisoning resistance and the like, so that the application of the supported noble metal catalysts is limited to a certain extent. Research shows that the addition of rare earth and its oxide can raise the activity of catalyst, raise the heat stability of catalyst and improve the sulfur and lead resisting capacity of catalyst. The other type is a non-metal catalyst, mainly comprising a transition metal oxide catalyst, a reoxygenation catalyst (perovskite reoxygenation and spinel reoxygenation) and the like, wherein the catalyst has higher ignition temperature although the high-temperature stability is slightly good. The basic requirements of VOCs catalytic combustion on the catalyst are: the catalyst has good low-temperature catalytic activity, good hydrothermal stability and high-temperature stability, and has good capability of resisting frequent heat load impact and carbon deposition.
The catalyst adopted in the catalytic method at present often needs to heat the material flow to the ignition temperature (200-400 ℃), and the VOCs are catalyzed and non-catalyzed to react to generate carbon dioxide and water, and the catalyst capable of catalyzing and igniting the VOCs at normal temperature to realize self-sustaining combustion is needed in the market.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-temperature-resistant catalytic combustion catalyst for self-sustaining combustion of VOCs under normal temperature catalytic ignition. In particular to a high-temperature resistant catalytic combustion catalyst for catalyzing and igniting VOCs at normal temperature to perform self-sustaining combustion, and a preparation method and application thereof. The catalyst of the invention can catalyze and ignite VOCs material flow containing a certain amount of low unsaturated hydrocarbon and hydrogen at the temperature of more than or equal to 30 ℃, has good hydrothermal stability and high temperature stability, and still has good catalytic combustion activity after 1000 ℃ accelerated aging.
The invention aims at providing a high-temperature resistant catalytic combustion catalyst for self-sustaining combustion of VOCs under normal temperature catalytic ignition, which can comprise a noble metal active component, an oxygen storage material cerium-zirconium solid solution and a carrier; the carrier comprises Al 2 O 3 A carrier;
wherein, based on 100 weight parts of the total weight of the catalyst, the content of the noble metal active component is 0.03 to 5 weight parts, preferably 0.05 to 3 weight parts, more preferably 0.05 to 1.5 weight parts, the content of the cerium-zirconium solid solution of the oxygen storage material is 5 to 40 weight parts, preferably 10 to 30 weight parts, and the rest is the carrier.
Wherein the noble metal active component is selected from Pd and/or Pt.
The oxygen storage material cerium-zirconium solid solution is cerium-zirconium solid solution which is formed by cerium-zirconium molar ratio (Ce/Zr) of 0.5-3 and through high-temperature solid phase reaction at 500-1200 ℃ (preferably 700-900 ℃).
The carrier comprises large surface Al 2 O 3 A carrier; the Al is 2 O 3 The specific surface of the carrier can be 100-300 m 2 /g。
The preparation method of the cerium-zirconium solid solution comprises the following steps:
and (3) weighing cerium salt and zirconium salt according to the molar ratio of cerium to zirconium, dissolving the cerium salt and the zirconium salt in an aqueous solution to prepare a mixed solution with the total concentration of solutes of 0.1-5 mol/L (preferably 0.2-2 mol/L), diluting 25wt% of ammonia water to 0.1-10 wt% (preferably 1-5 wt%) as a precipitator, putting the mixed solution into a three-neck flask, slowly dripping the mixed solution of cerium salt and zirconium salt under the condition of intense stirring until the PH value of the solution is 9-11, continuing stirring after the dripping is finished, standing overnight, washing and filtering with deionized water, drying a filter cake, and then programming to 500-1200 ℃, preferably roasting at 700-900 ℃ under flowing air to prepare the catalyst auxiliary agent.
The cerium salt may be selected from cerium nitrate, cerium sulfate, and cerium acetate;
the zirconium salt may be selected from zirconyl nitrate, zirconium oxychloride, or zirconium tetrachloride.
The second purpose of the invention is to provide a preparation method of the high-temperature-resistant catalytic combustion catalyst for self-sustaining combustion of the normal-temperature catalytic ignition VOCs. The method can be specifically selected from common wet forming methods.
The wet forming method specifically comprises the following steps:
cerium-zirconium solid solution of oxygen storage material, auxiliary agent and Al 2 O 3 The carrier and the forming auxiliary agent are kneaded, extruded and formed, dried for 3 to 10 hours at the temperature of 80 to 120 ℃ and baked for 3 to 5 hours at the temperature of 250 to 600 ℃ to prepare the catalyst carrier, and then impregnated with the required noble metal active component in an equal volume, dried for 3 to 10 hours at the temperature of 80 to 120 ℃ and baked for 3 to 5 hours at the temperature of 250 to 600 ℃.
The forming aid can be selected from binders, extrusion aids and the like; the shaping may be in the shape of a bar, raschig ring, honeycomb, etc. The dosage of the forming auxiliary agent can be Al 2 O 3 The weight of the carrier is 0.5-3%, and the carrier can be adjusted according to actual conditions.
The auxiliary agent is selected from sol; the sol can be at least one selected from titanium sol, silica sol, water glass and silane. The dosage of the auxiliary agent is Al 2 O 3 1 to 5 percent of the weight of the carrier.
The invention further aims to provide application of the high-temperature-resistant catalytic combustion catalyst for self-sustaining combustion of normal-temperature catalytic ignition VOCs in normal-temperature catalytic ignition of VOCs flow.
Wherein the VOCs stream may comprise low unsaturation VOCs off-gas and hydrogen;
the low unsaturated hydrocarbon may comprise C2-C4 alkene, alkyne, diene, etc.;
the low unsaturation hydrocarbon may comprise 10 to 60% by volume of the VOCs stream;
the hydrogen may comprise 5 to 20% by volume of the VOCs stream.
The constant temperature catalytic ignition VOCs self-sustaining combustion catalyst provided by the invention takes noble metal as an active component, cerium-zirconium solid solution as an auxiliary agent and alumina with a large specific surface as a carrier.
The essential difference between the invention and the prior art is that: the catalyst of the invention can catalyze and ignite VOCs material flow containing a certain amount of low unsaturated hydrocarbon and hydrogen at the temperature of more than or equal to 30 ℃, and has good hydrothermal stability and high temperature stability.
The beneficial effects of the invention are as follows: the catalyst provided by the invention can ignite VOCs material flow containing a certain amount of low-unsaturated hydrocarbon and hydrogen at normal temperature (more than or equal to 30 ℃) and normal pressure, and realizes self-sustaining combustion. The catalyst can remove VOCs waste gas without external auxiliary heating energy, is quick and effective in ignition, has good hydrothermal stability and high-temperature stability, and greatly simplifies the treatment of treating the VOCs waste gas.
Detailed Description
The invention will be further illustrated with reference to the following examples. The present invention is not limited by these examples.
Example 1
43g of cerium nitrate and 27g of zirconyl nitrate are weighed to prepare 0.25mol/L aqueous solution, 85g of 25wt% ammonia water is diluted to 5wt% and is taken as a precipitator to be placed in a three-neck flask, the mixed solution of cerium nitrate and zirconyl nitrate is slowly dripped into the three-neck flask under the condition of intense stirring until the PH value of the solution is 9-11, the mixed solution is continuously stirred for 0.5h after dripping, the mixed solution is stood and aged overnight, deionized water is used for washing and filtering, a filter cake is dried for 5h at 100 ℃, and then the mixed solution is baked for 5h at 900 ℃ under the condition of flowing air, so that the catalyst auxiliary agent cerium zirconium solid solution CZ1 is prepared. CZ1 was mixed with a specific surface area of 250m 2 Alumina (model 80150, from the scientific and technological company of Bo's kernel alumina Co., ltd.) (wherein the weight ratio of CZ1 to alumina is 3:7), silica sol aid (JH-40, from the chemical company of Jiangyin, soft fly Co., ltd.) (3% by weight of alumina), binder (1.5% by weight of alumina) and extrusion aid (1% by weight of alumina) were kneaded and extruded into strands, and dried at 100℃for 3.h, roasting for 2h at 450 ℃ to obtain a catalyst carrier CZ1-Al 2 O 3 . Catalyst support CZ1-Al 2 O 3 The palladium nitrate is impregnated by an isovolumetric impregnation method to ensure that the Pd content of the catalyst is 0.1 percent, the catalyst is dried after impregnation and baked for 2 hours at 450 ℃ to obtain the finished catalyst A (the Pd is 0.1 percent and the cerium-zirconium solid solution CZ1 accounts for 30 percent by weight).
Example 2
Weighing 55g of cerium nitrate and 34g of zirconyl nitrate to prepare 0.25mol/L aqueous solution, diluting 85g of 25wt% ammonia water to 5wt% as a precipitator, putting the aqueous solution into a three-neck flask, slowly dripping the mixed solution of cerium nitrate and zirconyl nitrate under the condition of intense stirring until the PH value of the solution is 9-11, continuing stirring for 0.5h after dripping, standing and aging overnight, washing with deionized water, filtering, drying a filter cake at 100 ℃ for 5h, and then programming to 900 ℃ under flowing air to bake for 5h to prepare the catalyst auxiliary agent cerium zirconium solid solution CZ2. CZ2 was mixed with a specific surface area of 250m 2 Alumina (model 80150, manufactured by Technical Co., ltd.) (wherein the weight ratio of CZ2 to alumina is 3:7), silica sol aid (JH-40, manufactured by Gentle chemical Co., ltd., jiangyin, 3% by weight of alumina), binder (1.5% by weight of alumina), extrusion aid (1% by weight of alumina), kneading and extruding, drying at 100deg.C for 3h, and calcining at 450deg.C for 2h to obtain catalyst carrier CZ2-Al 2 O 3 . Catalyst support CZ2-Al 2 O 3 The palladium nitrate is impregnated by an isovolumetric impregnation method to ensure that the Pd content of the catalyst is 0.1 percent, the catalyst is dried after impregnation and baked for 2 hours at 450 ℃ to obtain the finished catalyst B (the Pd is 0.1 percent and the cerium-zirconium solid solution CZ2 accounts for 30 percent by weight).
Example 3
Weighing 55g of cerium nitrate and 34g of zirconyl nitrate to prepare 0.25mol/L aqueous solution, diluting 85g of 25wt% ammonia water to 5wt% as a precipitator, putting the aqueous solution into a three-neck flask, slowly dripping the mixed solution of cerium nitrate and zirconyl nitrate under the condition of intense stirring until the PH value of the solution is 9-11, continuously stirring for 0.5h after dripping, standing and aging overnight, washing and filtering with deionized water, drying a filter cake at 100 ℃ for 5h, and flowing the solutionAnd (3) heating to 750 ℃ under a programmed condition in moving air, and roasting for 5 hours to prepare the catalyst promoter cerium-zirconium solid solution CZ3. CZ3 was mixed with a specific surface area of 250m 2 The catalyst carrier CZ3-Al is obtained by kneading/g alumina (model 80150, manufactured by Technical Co., ltd., wherein the weight ratio of CZ3 to alumina is 3:7) and silica sol auxiliary agent (JH-40, manufactured by Gentle Fei chemical Co., ltd., jiangyin Co., ltd.) (the amount is 3% of the weight of alumina), binder (1.5% of the weight of alumina) and extrusion aid (1% of the weight of alumina) to form a rod, drying at 100deg.C for 3h, and calcining at 450 ℃ for 2h 2 O 3 . Catalyst support CZ3-Al 2 O 3 The palladium nitrate is impregnated by an isovolumetric impregnation method to ensure that the Pd content of the catalyst is 0.1 percent, the catalyst is dried after impregnation and baked for 2 hours at 450 ℃ to obtain the finished catalyst C (the Pd is 0.1 percent and the cerium-zirconium solid solution CZ3 accounts for 30 percent by weight).
Example 4
Weighing 55g of cerium nitrate and 34g of zirconyl nitrate to prepare 0.25mol/L aqueous solution, diluting 85g of 25wt% ammonia water to 5wt% as a precipitator, putting the aqueous solution into a three-neck flask, slowly dripping the mixed solution of cerium nitrate and zirconyl nitrate under the condition of intense stirring until the PH value of the solution is 9-11, continuing stirring for 0.5h after dripping, standing and aging overnight, washing with deionized water, filtering, drying a filter cake at 100 ℃ for 5h, and then programming to 750 ℃ under flowing air to bake for 5h to prepare the catalyst auxiliary agent cerium zirconium solid solution CZ4. CZ4 was mixed with a specific surface area of 250m 2 The catalyst carrier CZ3-Al is obtained by kneading/g alumina (model 80150, manufactured by Technical Co., ltd., wherein the weight ratio of CZ4 to alumina is 12:88) and silica sol auxiliary agent (JH-40, manufactured by Gentle Fei chemical Co., ltd., jiangyin Co., ltd.) (the amount is 3% of the weight of alumina), binder (1.5% of the weight of alumina) and extrusion aid (1% of the weight of alumina) to form a rod, drying at 100deg.C for 3h, and calcining at 450 ℃ for 2h 2 O 3 . Catalyst support CZ3-Al 2 O 3 Impregnating palladium nitrate to make Pd content of catalyst be 0.1% by means of isovolumetric impregnation method, drying after impregnation, roasting at 450 deg.C for 2 hr, and recording to obtain the invented finished product catalyst D (Pd is 0.1% by weight, cerium-zirconium solid solution)CZ4 is 12%).
The light-off property, catalytic combustion performance and high temperature stability of the catalyst were evaluated in a fixed bed reactor. The catalyst dosage is 10mL, and the VOCs gas adopts V H2 ：V C2H4 ：V C3H6 ：V C3H8 ：V C4 =15:30:30:5:20, airspeed 10000h -1 VOCs gas is introduced during reaction, metered air is introduced after catalytic ignition, and V air: vvocs=18:1, the reaction is developed into self-sustaining catalytic combustion, and after the reaction temperature is stabilized for 30min, the tail gas is collected for gas chromatography analysis.
Comparative example 1
The catalyst was prepared in the same manner as in example 1 except that the Pd content of the catalyst was 0.02% by weight, and the catalyst thus obtained was designated as a.
Comparative example 2
The catalyst was prepared in the same manner as in example 1 except that cerium zirconium hydroxide was calcined at 500℃for 4 hours under an air atmosphere. The catalyst obtained is designated b.
Comparative example 3
The catalyst was prepared in the same manner as in example 1 except that the catalyst prepared by kneading and extruding CZ1 with alumina in a weight ratio of 1:1 was designated as c.
Comparative example 4
87g of cerium nitrate and 14g of zirconyl nitrate are weighed to prepare 0.25mol/L aqueous solution, 85g of 25wt% ammonia water is diluted to 5wt% and is taken as a precipitator to be placed in a three-neck flask, the mixed solution of cerium nitrate and zirconyl nitrate is slowly dripped into the three-neck flask under the condition of intense stirring until the PH value of the solution is 9-11, the mixed solution is continuously stirred for 0.5h after dripping, the mixed solution is stood and aged overnight, deionized water is used for washing and filtering, a filter cake is dried for 5h at 100 ℃, and then the temperature is programmed to 750 ℃ for roasting for 5h under flowing air, so that the catalyst auxiliary agent cerium zirconium solid solution CZ4 is prepared. CZ4 was mixed with a specific surface area of 250m 2 Alumina per g (type 80150 from the scientific and technological company of Bo's kernel alumina) (wherein the weight ratio of CZ4 to alumina is 12:88) and silica sol promoter (JH-40 from the chemical company of Jiangyin city (3% by weight of alumina)), binder (1.5% by weight of alumina) and extrusion promoter (amount ofKneading and extruding 1% of alumina to form, drying at 100deg.C for 3 hr, and calcining at 450deg.C for 2 hr to obtain catalyst carrier CZ4-Al 2 O 3 . Catalyst support CZ4-Al 2 O 3 Palladium nitrate was impregnated with an isovolumetric impregnation method to make the Pd content of the catalyst 0.1%, dried after impregnation, and calcined at 450 ℃ for 2 hours, and the catalyst thus prepared was designated as d (in weight percent: pd 0.1% and cerium zirconium solid solution CZ 4: 12%).
To examine the high temperature stability of the catalysts, the catalysts prepared in examples 1 to 4 and comparative examples 1 to 4 were calcined in air at 1000℃for 10 hours, and accelerated aging was performed, which were designated as A-acid, B-acid, C-acid, D-acid, a-acid, B-acid, C-acid, and D-acid, respectively, and the aged catalysts were subjected to further catalytic combustion performance evaluation, and the results are shown in Table 1.
The catalytic light-off and catalytic combustion effects of the catalyst are as follows.
Table 1 list of catalytic light-off temperatures for catalysts
TABLE 2 volume percent of VOCs gas after treatment (%)
* When the tail gas content is calculated by volume, the method does not contain N 2 、O 2 And H 2 O。
As can be seen from the data comparison of tables 1-2, the catalyst of the invention can be ignited at normal temperature and realize self-sustaining catalytic combustion, and has good catalytic combustion effect. The catalyst of the comparative example has a catalytic light-off temperature of about 200 ℃ and poor catalytic combustion effect. And after the catalyst is accelerated and aged for 5 hours at 1000 ℃, the ignition temperature of the catalyst is not obviously reduced, but the catalytic combustion effect is obviously reduced in the catalyst of the comparative example.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Claims (8)
1. The application of a high-temperature-resistant catalytic combustion catalyst capable of catalyzing and igniting VOCs at normal temperature to self-sustaining combustion in normal-temperature catalytic ignition of VOCs flow comprises a noble metal active component, an oxygen storage material cerium-zirconium solid solution and a carrier; the carrier comprises Al 2 O 3 A carrier;
wherein, based on 100 weight parts of the total weight of the catalyst, the content of noble metal active components is 0.05 to 3 weight parts, the content of cerium-zirconium solid solution of oxygen storage material is 10 to 30 weight parts, and the rest is carrier;
the noble metal active component is Pd and/or Pt;
the oxygen storage material cerium-zirconium solid solution is cerium-zirconium solid solution which is formed by cerium-zirconium molar ratio (Ce/Zr) of 0.5-3 and through high-temperature solid phase reaction at 500-1200 ℃;
the catalyst can ignite VOCs material flow at normal temperature and normal pressure and realize self-sustaining combustion; the normal temperature is more than or equal to 30 ℃;
the VOCs stream comprises low unsaturated hydrocarbon VOCs off-gas and hydrogen; the low unsaturated hydrocarbon comprises at least one of C2-C4 alkene, alkyne and diene;
the low unsaturated hydrocarbon accounts for 10-60% of the volume of the VOCs stream;
the hydrogen comprises 5 to 20% by volume of the VOCs stream.
2. The use according to claim 1, characterized in that: the oxygen storage material cerium-zirconium solid solution is prepared by a method comprising the following steps:
cerium salt and zirconium salt are weighed according to the cerium-zirconium molar ratio and dissolved in water to prepare a mixed solution with the total solute concentration of 0.1-5 mol/L; dropping the mixed solution into the precipitant under vigorous stirring until the pH value of the reaction solution is 9-11, continuing stirring, standing, washing, filtering, drying a filter cake, then programming to be heated to 500-1200 ℃ under flowing air, and roasting to prepare the cerium-zirconium solid solution;
the precipitant is selected from ammonia water with the concentration of 0.1-10wt%.
3. The use according to claim 2, characterized in that:
the oxygen storage material cerium-zirconium solid solution is prepared by a method comprising the following steps:
cerium salt and zirconium salt are weighed according to the cerium-zirconium molar ratio and dissolved in water to prepare a mixed solution with the total solute concentration of 0.2-2 mol/L; dropping the mixed solution into the precipitant under vigorous stirring until the pH value of the reaction solution is 9-11, continuing stirring, standing, washing, filtering, drying a filter cake, and then heating to 700-900 ℃ under flowing air for roasting to prepare the cerium-zirconium solid solution;
the precipitant is selected from ammonia water with the concentration of 1-5 wt%.
4. The use according to claim 2, characterized in that:
the cerium salt is selected from cerium nitrate, cerium sulfate and cerium acetate;
the zirconium salt is selected from zirconyl nitrate, zirconium oxychloride, or zirconium tetrachloride.
5. The use according to claim 1, characterized in that:
the Al is 2 O 3 The specific surface of the carrier is 100-300 m 2 /g。
6. Use according to any one of claims 1 to 5, characterized in that:
the preparation method of the catalyst is selected from wet forming methods;
the wet forming method comprises the following steps:
cerium-zirconium solid solution of oxygen storage material, auxiliary agent and Al 2 O 3 The carrier and the forming auxiliary agent are kneaded, extruded and formed, dried at 80-120 ℃, baked at 250-600 ℃ to obtain the catalyst carrier, impregnated with the required noble metal active component, dried at 80-120 ℃ and baked at 250-600 ℃.
7. The use according to claim 6, characterized in that:
the auxiliary agent is selected from sol; the sol is at least one selected from titanium sol, silica sol, water glass and silane.
8. The use according to claim 7, characterized in that:
the dosage of the auxiliary agent is the Al 2 O 3 1 to 5 percent of the weight of the carrier.
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| US20120003132A1 (en) * | 2009-07-23 | 2012-01-05 | Shudong Wang | Process for catalytic deoxygenation of coal mine methane |
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