CN115121110B - Method for catalyzing decomposition of nitrous oxide - Google Patents
Method for catalyzing decomposition of nitrous oxide Download PDFInfo
- Publication number
- CN115121110B CN115121110B CN202110312087.6A CN202110312087A CN115121110B CN 115121110 B CN115121110 B CN 115121110B CN 202110312087 A CN202110312087 A CN 202110312087A CN 115121110 B CN115121110 B CN 115121110B
- Authority
- CN
- China
- Prior art keywords
- carbon
- catalyst
- nickel
- nanocomposite
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/402—Dinitrogen oxide
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Abstract
The application relates to a method for catalyzing nitrous oxide decomposition, which comprises the steps of carrying out catalytic decomposition reaction by adopting a catalyst to contact with nitrous oxide, wherein the catalyst comprises a carrier, an active component and an auxiliary agent, wherein the active component is a carbon-coated nickel nanocomposite, the nanocomposite comprises a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer, and the inner core is nickel nanoparticles; the auxiliary agent comprises a second metal oxide, wherein the second metal oxide is an oxide of alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to nickel is 0.01-0.3. The method has excellent effect on catalyzing and decomposing nitrous oxide, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of catalytic chemistry, in particular to a method for catalyzing decomposition of nitrous oxide.
Background
Magnetic metallic nickel nanoparticles are receiving a great deal of attention due to their excellent optical, electrical, and magnetic properties. However, the metallic nickel nano particles have high activity, are easy to agglomerate or oxidize and even burn in the air, and greatly influence the performance and application of the materials. Meanwhile, as a nonmetallic material, the nano carbon material has the advantages of acid and alkali corrosion resistance, good conductivity, good chemical/electrochemical stability, high structural strength and the like. The carbon material is used for coating the nano particles of the active metal, so that the conductivity and the stability of the nano material can be effectively improved, and the limited domain of the nano particles is not easy to oxidize and agglomerate. In recent years, nanocarbon-coated metal composites have become a focus of attention. The material takes a single-layer to a plurality of curved graphitized carbon layers as a shell to tightly wrap the metal nano particles of the inner core, so that the nano particles are isolated from the outside, and the stability of the composite material is greatly improved. Therefore, the unique core-shell structure nano material has wide application prospect in the fields of catalytic materials, wave absorbing materials, information storage materials, magneto-optical materials, biomedical materials, lubricating oil additives and the like.
N 2 O is an important greenhouse gas, and its Global Warming Potential (GWP) is CO 2 310 times of CH 4 21 times of (2); in addition, N 2 The average life of O in the atmosphere is about 150 years, also the NO in the stratosphere x The main source of the composition is not only capable of seriously destroying the ozone layer, but also has strong greenhouse effect.
The domestic adipic acid production mainly adopts a cyclohexanol nitric acid oxidation method, and the cyclohexanol is subjected to nitric acid oxidation to produce adipic acid, the technology of the method is mature, the product yield and purity are relatively high, but the nitric acid consumption is large, and a large amount of N is produced in the reaction process 2 O, and the tail gas discharged in the production process is concentrated, large in quantity and high in concentration (36% -40%). At present, 15 ten thousand tons of adipic acid and N are produced annually by adopting a cyclohexanol nitric acid oxidation method 2 The annual discharge of O can reach 4.5 ten thousand tons. Therefore, the tail gas of the adipic acid purifying device can effectively control and eliminate N 2 O has become a research hotspot in the field of environmental catalysis today.
The direct catalytic decomposition method can decompose N 2 O is decomposed into nitrogen and oxygen to eliminate N 2 O is the most effective and clean technique. Wherein, the catalyst is the technical core of the direct catalytic decomposition method. Decomposition N reported in the current study 2 The catalyst of O mainly comprises a noble metal catalyst, an ion-exchange molecular sieve catalyst and a transition metal oxide catalyst. Noble metal catalysts (e.g., rh and Ru) on N 2 The O catalytic decomposition has higher low-temperature catalytic activity (the temperature is 250-350 ℃ and N can be efficiently decomposed) 2 O), the expensive price limits the large-scale use of noble metal catalysts. Molecular sieve-type catalysts and transition metal oxide catalysts are significantly less expensive than noble metals, but currently these two types of catalysts are relatively more expensive than noble metals for N 2 The activity of O catalytic decomposition is low, and the high-efficiency decomposition temperature is 450-550 ℃. Thus, new materials catalyst pair N was developed that are new non-noble metals, low cost and efficient 2 The emission reduction of O has important significance.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
It is a main object of the present invention to overcome at least one of the above-mentioned drawbacks of the prior art and to provide a method for catalytically decomposing nitrous oxide, wherein the catalyst used in the method comprises carbon-coated nickel doped with alkali metal and/or alkaline earth metal, and the carbon-coated nickel nanocomposite is used as a raw powder, and the raw powder is processed by a specific process to obtain a catalyst having excellent catalytic activity and good mechanical properties, which can meet industrial application requirements, and particularly has a better effect on catalytically decomposing nitrous oxide after doping with alkali metal and/or alkaline earth metal, and has good industrial application prospects.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for catalyzing the decomposition of nitrous oxide comprises the steps of adopting a catalyst to contact with nitrous oxide for catalytic decomposition reaction to generate nitrogen and oxygen, wherein the catalyst comprises a carrier, an active component and an auxiliary agent which are loaded on the carrier,
the active component is a carbon-coated nickel nanocomposite, the nanocomposite comprises a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer, and the inner core is nickel nano particles;
the auxiliary agent comprises a second metal oxide, wherein the second metal oxide is an oxide of alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to nickel is 0.01-0.3.
In one embodiment, the nickel is present in an amount of 16% to 76%, the support is present in an amount of 10% to 60%, and the carbon is present in an amount of 6% to 54% based on the weight of the catalyst.
In one embodiment, the catalyst is prepared by the steps of:
providing a carbon-coated nickel nanocomposite as raw powder, preparing a second metal salt solution, uniformly mixing the carbon-coated nickel nanocomposite with the second metal salt solution, and stirring to obtain a solid-liquid mixture; drying and first roasting the solid-liquid mixture to obtain solid powder; adding a binder into the solid powder, and uniformly mixing to obtain a wet dough;
the wet dough is subjected to forming treatment, the formed body is dried, and then the second roasting treatment is carried out in inert atmosphere, so that the catalyst of carbon-coated nickel is obtained;
wherein the second metal salt solution is selected from alkali metal salt solutions and/or alkaline earth metal salt solutions.
In one embodiment, the first firing process includes: heating the dried solid-liquid mixture to 200-500 ℃ at a heating rate of 1-20 ℃/min, and keeping the constant temperature for 0.5-10 h; the second firing treatment includes: heating the product after the molding treatment to 400-800 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature for 1-10 h.
In one embodiment, the binder is an aluminum sol, a silica sol, or a silica alumina sol.
In one embodiment, the binder is made from pseudo-boehmite and a peptizing agent selected from one or more of aqueous nitric acid, aqueous hydrochloric acid, and aqueous citric acid.
In one embodiment, the binder further comprises a lubricant selected from one or more of sesbania powder, citric acid, starch, and carboxymethyl cellulose; the mass of the lubricant is 1-6% of the mass of the raw powder.
In one embodiment, the mass ratio of liquid to solid in the wet dough is 0.8 to 1.5:1, the raw powder accounts for 20-80% of the mass of the solid in the wet dough.
In one embodiment, the drying temperature is 20 ℃ to 100 ℃, the drying time is 3 hours to 24 hours, and the drying atmosphere is an inert atmosphere or an air atmosphere.
In one embodiment, the shaping treatment is selected from one or more of extrusion, rolling, and pelletization.
In one embodiment, the carbon-coated nickel nanocomposite comprises a core-shell structure having a shell layer and an inner core, the shell layer being a graphitized carbon layer, the inner core being nickel nanoparticles, the carbon content being 15wt% to 60wt% and the nickel content being 40wt% to 85wt%, based on the weight of the carbon-coated nickel nanocomposite.
In one embodiment, in the catalytic decomposition reaction, the reaction temperature is 300-420 ℃, the reaction space velocity is 500-3000 ml of reaction gas/(hr-g of catalyst), and the volume concentration of the nitrous oxide is 30% -40%.
According to the technical scheme, the beneficial effects of the invention are as follows:
compared with the existing catalyst, the N in the industrial waste gas must be reduced 2 O is diluted and then treated, the catalyst of the method can directly catalyze and decompose high-concentration nitrous oxide waste gas generated in industrial production at a lower temperature, the decomposition rate can reach more than 99%, and the catalyst has great significance for protecting environment and reducing atmospheric pollution and has good industrial application prospect. The catalyst used in the method of the invention obtains the carbon with unique structure and composition by taking the nano composite material of the carbon-coated nickel as the raw powderNickel-coated catalyst, which is furthermore doped with a second metal, i.e. an alkali metal and/or an alkaline earth metal, which catalyzes N 2 The O decomposition reaction may be characterized by further improvement in catalytic activity.
Drawings
The following drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain the invention, without limitation to the invention.
FIG. 1 is an X-ray diffraction chart of the product obtained in the step (2) of example 1;
FIG. 2 is a transmission electron micrograph of the product obtained in step (2) of example 1;
FIG. 3 is an X-ray diffraction pattern of the product obtained in the step (2) of example 2;
FIG. 4 is a transmission electron micrograph of the product obtained in step (2) of example 2.
Detailed Description
The following provides various embodiments or examples to enable those skilled in the art to practice the invention as described herein. These are, of course, merely examples and are not intended to limit the invention from that described. The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
The application provides a method for catalyzing nitrous oxide decomposition, which comprises the steps of adopting a catalyst to contact with nitrous oxide for catalyzing and decomposing reaction to generate nitrogen and oxygen, wherein the catalyst comprises a carrier, an active component and an auxiliary agent which are loaded on the carrier,
the active component is a carbon-coated nickel nanocomposite, the nanocomposite comprises a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer, and the inner core is nickel nano particles;
the auxiliary agent comprises a second metal oxide, wherein the second metal oxide is an oxide of alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to nickel is 0.01-0.3.
A catalyst for carbon-coated nickel used in the method of the present application comprises a carrier, an active component and an auxiliary agent supported on the carrier,
the active component is a carbon-coated nickel nanocomposite, the nanocomposite comprises a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer, and the inner core is nickel nano particles;
the auxiliary agent comprises a second metal oxide, wherein the second metal oxide is an oxide of alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to nickel is 0.01-0.3.
In one embodiment, the nickel is present in an amount of 16% to 76%, the support is present in an amount of 10% to 60%, and the carbon is present in an amount of 6% to 54% based on the weight of the catalyst.
According to the invention, the aforementioned support may be alumina and/or silica. The catalyst has a pore structure, and in some embodiments, the catalyst of the invention has a specific surface area of 150m 2 /g～240m 2 Per gram, pore volume of 0.30cm 3 /g～0.50cm 3 And/g, the crushing strength is 50N/cm-120N/cm. In one embodiment, the amount of support may be 10% to 50%,10% to 40%,10% to 35%, or 10% to 30% based on the weight of the catalyst.
The catalyst can further improve the performance of the catalyst by further improving the carbon-coated nickel nanocomposite and adding an auxiliary agent.
In this application, the carbon-coated nickel nanocomposite as the catalyst active component has a core-shell structure having a shell layer and an inner core, the shell layer being a graphitized carbon layer, the inner core being nickel nanoparticles, the carbon content being 15wt% to 60wt% and the nickel content being 40wt% to 85wt% based on the weight of the carbon-coated nickel nanocomposite. In one embodiment, the carbon-coated nickel nanocomposite may have a particle size of 1 to 100nm, preferably 2 to 40nm.
The carbon-coated nickel nanocomposite can be obtained from commercial sources or can be prepared by the following method:
placing a nickel source and carboxylic acid in a solvent and mixing to form a homogeneous solution; removing the solvent in the homogeneous solution to obtain a precursor; and pyrolyzing the precursor in inert atmosphere or reducing atmosphere to obtain the carbon-coated nickel nanocomposite.
Specifically, the precursor is a water-soluble mixture, which is obtained by dissolving a nickel source and carboxylic acid in a solvent such as water, ethanol, etc. to form a homogeneous solution, and then directly evaporating the solvent to remove the nickel. The aforementioned temperature and process of evaporating the solvent may be any available prior art technique, for example, spray drying at 80-120 ℃, or drying in an oven.
In some embodiments, the nickel source is selected from one or more of a soluble organic acid salt, a basic carbonate, a hydroxide, and an oxide of nickel, the carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, gluconic acid, and malic acid, and the mass ratio of the nickel source to the carboxylic acid is 1 (0.1-10). In addition, other organic compounds than the two above may be added together to form a homogeneous solution, and the other organic compounds may be any organic compound that can supplement the carbon source required in the product and that does not contain other doping atoms. Organic compounds which are not volatile, such as organic polyols, lactic acid, etc., are preferred. In some embodiments, the mass ratio of nickel source, carboxylic acid, and other organic compounds is 1:0.1-10:0-10, preferably 1:0.5-5:0-5, more preferably 1:0.8-3:0-3.
In some embodiments, pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section; wherein the heating rate is 0.5-30 ℃/min, such as 2.5 ℃/min, 4.5 ℃/min, 5 ℃/min, 6.5 ℃/min, 7 ℃/min, 8.5 ℃/min, 9 ℃/min, 10 ℃/min, 20 ℃/min, etc.; the constant temperature section temperature is 400-800 ℃, preferably 500-700 ℃, such as 500 ℃, 550 ℃, 570 ℃, 610 ℃, 660 ℃, 680 ℃, and the like; the constant temperature is maintained for 20 min-600 min, preferably 30 min-300 min, such as 30min, 45min, 55min, 70min, 86min, 97min, 100min, 180min, 270min, 300min, etc.; the inert atmosphere is nitrogen or argon, the reducing atmosphere is a mixed gas of inert gas and hydrogen, for example, a small amount of hydrogen is doped in the inert atmosphere.
The carbon-coated nickel nanocomposite can be obtained by the above method, and of course, the carbon-coated nickel nanocomposite can be prepared by other methods, which is not limited thereto.
In some embodiments, the invention further comprises acid washing the carbon-coated nickel nanocomposite obtained after the pyrolysis described above. The nanocomposite is a nickel-coated graphitized carbon layer nanocomposite. The term "graphitized carbon layer" refers to a carbon structure in which a layered structure is clearly observed under a high resolution transmission electron microscope, not an amorphous structure, and the interlayer spacing is about 0.34nm. The nano composite material with the graphitized carbon layer coated with nickel is a composite material composed of nickel nano particles tightly coated with the graphitized carbon layer (not in contact with the outside), nickel nano particles capable of being in contact with the outside and limited in domain and a carbon material with a mesoporous structure. After pickling treatment, nickel in the composite material has a certain loss, and can be characterized by a pickling loss rate. That is, "pickling loss" refers to the loss ratio of nickel after pickling of the finished carbon-coated nickel nanocomposite product. Reflecting how tightly the graphitized carbon layer coats the nickel. If the graphitized carbon layer does not cover the nickel tightly, the nickel of the inner core is dissolved by the acid after the acid treatment and is lost. The higher the acid washing loss rate, the lower the tightness degree of the graphitized carbon layer on the nickel coating is, and the lower the acid washing loss rate is, the higher the tightness degree of the graphitized carbon layer on the nickel coating is.
In general, specific conditions for the acid washing treatment are: 1g of the sample was added in a proportion of 20mL of an aqueous sulfuric acid solution (1 mol/L), the sample was treated at 90℃for 8 hours, then washed with deionized water to neutrality, dried, weighed, analyzed, and the acid washing loss rate was calculated as follows.
The calculation formula is as follows: the pickling loss rate= [1- (mass fraction of nickel in the composite after pickling x mass of the composite after pickling)/(mass fraction of nickel in the composite to be treated x mass of the composite to be treated) ] ×100%. In some embodiments, the composite material generally has a pickling loss of 60% or less, may be 40% or less, may be 30% or less, may be 20% or less, and may be 10% or less.
In some common chemical processes, such as fixed bed processes, not only are certain activities and selectivities required of the catalysts, but also certain requirements on the properties of particle size, mechanical strength and the like are required. The catalyst particles are too small or disintegrated and pulverized due to insufficient strength, so that the catalyst is easy to carry loss or block the device in the reaction process, the pressure drop of the catalyst bed is greatly increased, and even the device is forced to stop. The carbon-coated nano material has small particles, powder shape and poor self-forming property, and if the carbon-coated nano material is applied to the processes, the carbon-coated nano material must be subjected to forming treatment to meet the industrial reaction requirements of compressive strength, pressure drop after filling, stability and the like. The molding process is a process of forming solid particles having a certain size, shape and mechanical strength by mutually aggregating raw materials such as a catalyst raw powder and a molding aid by an external force. The molding process can have an effect on the activity, strength and service life of the catalyst to a certain extent. How to improve the mechanical strength of the catalyst and simultaneously maintain the catalytic performance of the carbon-coated nano material as much as possible is the research focus of the forming method of the carbon-coated nano material.
For the catalysts of the present application, the carbon-coated nickel nanocomposite may be further shaped by a method comprising the steps of:
providing a carbon-coated nickel nanocomposite as raw powder, preparing a second metal salt solution, uniformly mixing the carbon-coated nickel nanocomposite with the second metal salt solution, and stirring to obtain a solid-liquid mixture; drying and first roasting the solid-liquid mixture to obtain solid powder; adding a binder into the solid powder, and uniformly mixing to obtain a wet dough;
the wet dough is subjected to forming treatment, the formed body is dried, and then the second roasting treatment is carried out in inert atmosphere, so that the catalyst of carbon-coated nickel is obtained;
wherein the second metal salt solution is selected from alkali metal salt solutions and/or alkaline earth metal salt solutions.
Specifically, in the method of the application, the carbon-coated nickel nanocomposite is taken as raw powder, a second metal salt solution is prepared, the carbon-coated nickel nanocomposite and the second metal salt solution are uniformly mixed and stirred for 1-4 hours to obtain a solid-liquid mixture, the solid-liquid mixture is dried and roasted for the first time to obtain solid powder, and in the process, the second metal salt is doped into the raw powder through impregnation; and adding a binder into the solid powder, and uniformly mixing to obtain a wet dough.
In one embodiment, the solvent of the second metal salt solution of the above process may be water, and the second metal salt solution may be selected from one or more of an organic acid salt solution of an alkali metal and/or an alkaline earth metal, a carbonate solution, a basic carbonate solution, a nitrate solution, and a sulfate solution, preferably, a potassium nitrate solution or a potassium carbonate solution. In this process, the addition amount of the second metal salt solution may be controlled so that the molar ratio of the second metal to nickel is 0.01 to 0.3, or 0.01 to 0.2.
In one embodiment, the drying temperature of the above process is 20 ℃ to 100 ℃, the drying time is 3 hours to 24 hours, and the drying atmosphere is an inert atmosphere or an air atmosphere.
In one embodiment, the first firing treatment of the above process includes: heating the dried solid-liquid mixture to 200-500 ℃ at a heating rate of 1-20 ℃/min, and keeping the constant temperature for 0.5-10 h.
In one embodiment, the binder may be an aluminum sol, a silica sol, or a silica alumina sol. Further, the binder may be prepared from pseudo-boehmite and a peptizing agent selected from one or more of aqueous nitric acid, aqueous hydrochloric acid and aqueous citric acid. In one embodiment, the binder may further comprise a lubricant selected from one or more of sesbania powder, citric acid, starch and carboxymethyl cellulose, and the mass of the lubricant is 1 to 6% of the mass of the raw powder.
In one embodiment, the mass ratio of liquid to solid in the wet mass may be 0.8 to 1.5:1, the raw powder accounts for 20-80% of the mass of the solid in the wet dough. In some embodiments, the liquid to solid mass ratio in the wet dough is 0.8 to 1.5, for example 0.8, 0.9, 1, 1.2, etc., preferably 0.85 to 1. The raw powder accounts for 20% -80% of the solid mass in the wet dough, such as 20%, 25%, 31%, 47%, 56%, 60%, 75% and the like. The binder accounts for 20% -80% of the solid mass in the wet dough, such as 22%, 36%, 41%, 47%, 55%, 67%, 80% and the like; the mass of the lubricant is 1% to 6% of the mass of the raw powder, for example, 1%, 2%, 4%, 5%, 6% and the like, preferably 2% to 3%.
After the wet dough of the desired composition is obtained, the wet dough is subjected to a shaping treatment, wherein the shaping treatment method is one or more of extrusion, rolling and granulation, and the present invention is not limited thereto.
After the molding treatment, the obtained molded article is dried at a drying temperature of 20 to 100 ℃, for example, 20 ℃, 25 ℃, 30 ℃,40 ℃, 50 ℃, 65 ℃, 70 ℃, 72 ℃, 82 ℃, 88 ℃, and the like. The drying time is 3h to 24h, for example 3h, 4h, 6h, 7h, 10h, 12h, 13h, 17h, 20h, 24h, etc. The drying atmosphere is an inert atmosphere or an air atmosphere.
After the drying process, the resulting product is further subjected to a second calcination process under an inert atmosphere of nitrogen, an inert gas in the usual sense, or other non-oxidizing gas. In one embodiment, the second firing process includes: heating the product after the molding treatment to 400-800 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature for 1-10 h.
Thus, a carbon-coated nickel catalyst of the present application can be obtained. The catalyst comprises a carrier, an active component and an auxiliary agent, wherein the active component and the auxiliary agent are loaded on the carrier, the active component is a carbon-coated nickel nanocomposite, and the nanocomposite comprises a shell layer and an inner coreThe core-shell structure is characterized in that the shell layer is a graphitized carbon layer, the inner core is nickel nano particles, the auxiliary agent comprises a second metal oxide, the second metal oxide is an oxide of alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to the nickel is 0.01-0.3. According to the invention, the aforementioned support may be alumina and/or silica. The catalyst has a pore structure, and in some embodiments, the catalyst of the invention has a specific surface area of 150m 2 /g～240m 2 Per gram, pore volume of 0.30cm 3 /g～0.50cm 3 And/g, the crushing strength is 50N/cm-120N/cm.
It should be noted that, for the present invention, the specific surface area, pore volume and crush strength ranges of the catalyst obtained by different binders (such as alumina sol, silica sol, pseudo-boehmite, etc.) and different molding conditions (such as pressure) and molding modes (extrusion, rolling ball, pelletization) are greatly different, so the present invention is not limited thereto, and the specific surface area, pore volume and crush strength ranges can be adjusted according to the actual operating conditions and the requirements for the catalyst strength.
The catalyst has good catalytic activity, particularly the activity of catalyzing the decomposition of nitrous oxide, so the application provides a method for catalyzing the decomposition of nitrous oxide by adopting the catalyst, and particularly, the gas containing nitrous oxide is introduced into a reactor provided with the catalyst for catalytic decomposition reaction to generate nitrogen and oxygen.
In some embodiments, the catalytic decomposition reaction is at a temperature of 300 ℃ to 420 ℃, preferably 360 ℃ to 420 ℃. The space velocity of the catalytic decomposition reaction is 500-3000 ml of reaction gas/(hr.g of catalyst). The high reaction space velocity allowed by the invention indicates that the catalyst has high activity and high device processing capacity when the reaction is applied.
According to the invention, as previously described, the decomposition N reported in the current research 2 The catalyst of O mainly comprises a noble metal catalyst, an ion-exchange molecular sieve catalyst and a transition metal oxide catalyst. Noble metal catalysts, although having a low decomposition temperature, are not suitable for large-scale industrial production at an expensive price; other molecular sieve based catalysts and transition metal oxidesThe high-efficiency decomposition temperature of the compound catalyst is 450-550 ℃, and the high temperature required by the reaction greatly improves the industrial cost.
The inventors of the present invention have found that the carbon-coated nickel catalyst of the present invention can effectively decompose nitrous oxide into nitrogen and oxygen, and exhibits excellent stability of catalytic activity in the reaction. In addition, when the existing catalyst is used for catalyzing and decomposing nitrous oxide, the high-concentration nitrous oxide obtained in industrial production is generally required to be diluted to about 0.5% -2%, and the catalyst can be directly decomposed to reach a high decomposition rate without dilution. Namely, the catalytic decomposition reaction can be carried out when the volume concentration of the nitrous oxide is 36-40%, and the decomposition rate can reach more than 99%, so that the industrial cost is greatly reduced, and the method has good industrial application prospect.
Accordingly, the present application relates to a method of catalyzing the decomposition of nitrous oxide comprising contacting nitrous oxide with a carbon-coated nickel catalyst of the present application to effect a catalytic decomposition reaction to produce nitrogen and oxygen. In one embodiment, in the catalytic decomposition reaction, the reaction temperature is 300-420 ℃, the reaction space velocity is 500-3000 ml of reaction gas/(hr-g of catalyst), and the volume concentration of the nitrous oxide is 30% -40%.
The invention will be further illustrated by the following examples, but the invention is not limited thereby. Unless otherwise indicated, all reagents used in the present invention were analytically pure.
Analysis of carbon (C) was performed on a Elementar Micro Cube elemental analyzer, which was used mainly for analysis of four elements, carbon (C), hydrogen (H), oxygen (O), and nitrogen (N), with the following specific methods and conditions: 1 mg-2 mg of sample is weighed in a tin cup, is put into an automatic sample feeding disc, enters a combustion tube through a ball valve for combustion, the combustion temperature is 1000 ℃ (in order to remove atmospheric interference during sample feeding, helium is adopted for blowing), and then reduction copper is used for reducing the burnt gas to form nitrogen, carbon dioxide and water. The mixed gas is separated by three desorption columns and sequentially enters a TCD detector for detection. The analysis of oxygen element is to convert oxygen in the sample into CO by pyrolysis under the action of a carbon catalyst, and then detect the CO by TCD. The raw powder carbon-coated nickel only contains carbon, hydrogen, oxygen and metallic nickel, so the total content of the metallic nickel can be known by the content of the carbon, hydrogen and oxygen elements.
The ratio of the different metal oxides in the catalyst is measured by an X-ray fluorescence spectrum analyzer (XRF), and the content of the different metal oxides in the composite material is calculated by the known content of carbon elements. The model of the X-ray fluorescence spectrum analyzer (XRF) adopted by the invention is Rigaku 3013X-ray fluorescence spectrum analyzer, and the X-ray fluorescence spectrum analysis test conditions are as follows: the scan time was 100s and the atmosphere was air.
The model of the high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100 (HRTEM) (Japanese electronics Co., ltd.) and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV.
The model of the XRD diffractometer adopted by the invention is XRD-6000 type X-ray powder diffractometer (Shimadzu), and XRD testing conditions are as follows: cu target, ka radiation (wavelength λ=0.154 nm), tube voltage 40kV, tube current 200mA, scan speed 10 ° (2θ)/min.
The invention detects the pore structure property of the material by a BET test method. Specifically, the specific surface area, the pore volume and the average pore diameter of the catalyst are measured by a Quantachrome AS-6B type analyzer, and the pore diameter is the most probable.
The crushing strength of the invention refers to the pressure of each catalyst when being crushed, the strength is measured by adopting a ZQJ-III type intelligent particle strength tester of a large-connection intelligent tester factory, and 20 catalysts in the same batch are randomly extracted, wherein the ratio of the particle size to the length is 1:1 to 1.5, taking the arithmetic average value of the maximum value and the minimum value as a Newton value F (N) when single particles are crushed after the maximum value and the minimum value are removed, and calculating the radial crushing strength sigma (N/cm) of the single particles according to a formula sigma=F/L, wherein L is the length (cm) of the single particles.
Example 1
This example is illustrative of the preparation of the catalyst of the present invention
(1) 10g of nickel carbonate and 10g of citric acid are weighed into a beaker containing 100mL of deionized water, stirred at 70 ℃ to obtain a homogeneous solution, and continuously heated and evaporated to dryness to obtain a solid precursor.
(2) And (3) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow of 100mL/min, heating to 600 ℃ at the speed of 4 ℃/min, stopping heating after keeping the temperature for 2 hours, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite. The elemental analysis shows that the mass percentages of the elements contained in the carbon-coated nickel nanocomposite are respectively as follows: 26.14% of carbon, 0.42% of hydrogen, 0.91% of oxygen and 72.53% of nickel.
As can be seen from fig. 1, the nickel in the material is present in a reduced form. Fig. 2 is a TEM image of a nanocomposite of the material, which can be seen to be a carbon-coated nickel nanocomposite, with a graphitized carbon layer coating the outer layer of the nickel nanoparticle, having a core-shell structure.
(3) Adding K 2 CO 3 The aqueous solution, in which the molar ratio of potassium to nickel was 0.01, was stirred for 2 hours, placed in an 80 ℃ oven and dried for 12 hours.
(4) Uniformly mixing pseudo-boehmite accounting for 50% of the total powder mass and the product obtained in the step (3) at room temperature, adding sesbania powder accounting for 1.5% of the mass of the raw powder, uniformly mixing, preparing nitric acid accounting for 2.5% of the mass of the pseudo-boehmite into 1mol/L nitric acid aqueous solution, dropwise adding, and continuously stirring until the materials are uniformly mixed, thus obtaining wet dough.
(5) The wet dough was formed by extruding with a circular orifice plate with a diameter of 3mm on an F-26 twin screw extruder (manufactured by general industrial works of the university of North China medical science) to obtain solid cylindrical bars, cutting the solid cylindrical bars into particles with a length of 3-4 mm, drying the solid cylindrical bars in an oven at 40 ℃ for 24 hours, then placing the solid cylindrical bars in a tube furnace, introducing nitrogen gas, heating to 600 ℃ at a rate of 5 ℃/min, keeping the temperature constant for 4 hours, stopping heating, cooling to room temperature under a nitrogen gas atmosphere to obtain cylindrical bar catalysts, and measuring the crushing strength, specific surface area and pore volume of the cylindrical bar catalysts, wherein the results are shown in Table 1. As is clear from XRF and elemental analysis, the molded catalyst had a carbon content of 16.82 wt%, a potassium oxide content of 0.41 wt%, a nickel content of 46.63 wt% and an alumina content of 36.14 wt%.
The specific surface area, pore volume, pore size and crush strength of the catalyst are shown in Table 1.
Example 2
(1) 10g of nickel acetate and 10g of citric acid are weighed into a beaker containing 100mL of deionized water, stirred at 70 ℃ to obtain a homogeneous solution, and continuously heated and evaporated to dryness to obtain a solid precursor.
(2) And (3) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow of 100mL/min, heating to 650 ℃ at the speed of 2 ℃/min, stopping heating after keeping the temperature for 2 hours, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite. Elemental analysis shows that the mass percentages of the elements contained in the carbon-coated nickel nanocomposite are respectively as follows: 24.29% of carbon, 0.47% of hydrogen, 0.96% of oxygen and 74.28% of nickel.
As can be seen from fig. 3, the nickel in the material is present in a reduced form. Fig. 4 is a TEM image of a nanocomposite of the material, which can be seen to be a carbon-coated nickel nanocomposite, with a graphitized carbon layer coating the outer layer of the nickel nanoparticle, with a core-shell structure.
(3) Adding K 2 CO 3 The aqueous solution, in which the molar ratio of potassium to nickel was 0.1, was stirred for 2 hours, placed in an 80 ℃ oven and dried for 12 hours.
(4) Uniformly mixing pseudo-boehmite accounting for 25% of the total powder mass and the product obtained in the step (3) at room temperature, adding sesbania powder accounting for 1.5% of the mass of the raw powder and uniformly mixing, preparing nitric acid accounting for 2.5% of the mass of the pseudo-boehmite into 1mol/L nitric acid aqueous solution, dropwise adding, and continuously stirring until the materials are uniformly mixed; wet dough is obtained.
(5) The wet dough was formed by extruding with a circular orifice plate with a diameter of 3mm on an F-26 twin screw extruder (manufactured by general industrial works of the university of North China medical science) to obtain solid cylindrical bars, cutting the solid cylindrical bars into particles with a length of 3-4 mm, drying the solid cylindrical bars in an oven at 40 ℃ for 24 hours, then placing the solid cylindrical bars in a tube furnace, introducing nitrogen gas, heating to 600 ℃ at a rate of 5 ℃/min, keeping the temperature constant for 4 hours, stopping heating, cooling to room temperature under a nitrogen gas atmosphere to obtain cylindrical bar catalysts, and measuring the crushing strength, specific surface area and pore volume of the cylindrical bar catalysts, wherein the results are shown in Table 1. As is clear from XRF and elemental analysis, the molded catalyst had a carbon content of 19.34 wt%, a potassium oxide content of 4.13 wt%, a nickel content of 58.91 wt% and an alumina content of 17.62 wt%.
The specific surface area, pore volume, crush strength of the catalyst are shown in Table 1.
Example 3
(1) K was added to the carbon-coated nickel nanocomposite obtained in step (2) of example 1 at room temperature 2 CO 3 The aqueous solution, in which the molar ratio of potassium to nickel was 0.1, was stirred for 2 hours, placed in an 80 ℃ oven and dried for 12 hours.
(2) Uniformly mixing pseudo-boehmite accounting for 25% of the total powder mass and the carbon-coated nickel nanocomposite obtained in the step (1) at room temperature, adding sesbania powder accounting for 1.5% of the mass of the raw powder and uniformly mixing, preparing nitric acid accounting for 2.5% of the mass of the pseudo-boehmite into 1mol/L nitric acid aqueous solution, dropwise adding, and continuously stirring until the materials are uniformly mixed to obtain wet dough;
(3) The wet dough was formed by extruding with a circular orifice plate with a diameter of 3mm on an F-26 twin screw extruder (manufactured by general industrial works of the university of North China medical science) to obtain solid cylindrical bars, cutting the solid cylindrical bars into particles with a length of 3-4 mm, drying the solid cylindrical bars in an oven at 40 ℃ for 24 hours, then placing the solid cylindrical bars in a tube furnace, introducing nitrogen gas, heating to 600 ℃ at a rate of 5 ℃/min, keeping the temperature constant for 4 hours, stopping heating, cooling to room temperature under a nitrogen gas atmosphere to obtain cylindrical bar catalysts, and measuring the crushing strength, specific surface area and pore volume of the cylindrical bar catalysts, wherein the results are shown in Table 1. As is clear from XRF and elemental analysis, the molded catalyst had a carbon content of 20.63 wt%, a potassium oxide content of 4.24 wt%, a nickel content of 58.02 wt% and an alumina content of 17.11 wt%.
The specific surface area, pore volume, crush strength of the catalyst are shown in Table 1.
Comparative example 1
The carbon-coated nickel nanocomposite obtained in step (2) of example 1 was used as a catalyst.
Comparative example 2
The carbon-coated nickel nanocomposite obtained in step (2) of example 2 was used as a catalyst.
Comparative example 3
(1) Uniformly mixing pseudo-boehmite accounting for 25% of the total powder mass and raw powder at room temperature by taking the carbon-coated nickel nanocomposite obtained in the step (2) of the example 2 as raw powder, adding sesbania powder accounting for 1.5% of the total powder mass, uniformly mixing, preparing nitric acid accounting for 2.5% of the total mass of the pseudo-boehmite into 1mol/L nitric acid aqueous solution, dropwise adding, and continuously stirring until the materials are uniformly mixed; wet dough is obtained.
(2) The wet dough was formed by extruding with a circular orifice plate with a diameter of 3mm on an F-26 twin screw extruder (manufactured by general industrial works of the university of North China medical science) to obtain solid cylindrical bars, cutting the solid cylindrical bars into particles with a length of 3-4 mm, drying the solid cylindrical bars in an oven at 40 ℃ for 24 hours, then placing the solid cylindrical bars in a tube furnace, introducing nitrogen gas, heating to 600 ℃ at a rate of 5 ℃/min, keeping the temperature constant for 4 hours, stopping heating, cooling to room temperature under a nitrogen gas atmosphere to obtain cylindrical bar catalysts, and measuring the crushing strength, specific surface area and pore volume of the cylindrical bar catalysts, wherein the results are shown in Table 1. As is evident from XRF and elemental analysis, the molded catalyst had a carbon content of 20.18 wt%, a nickel content of 61.05 wt% and an alumina content of 18.77 wt%. The specific surface area, pore volume, pore size and crush strength of the catalyst are shown in Table 1.
Application example 1
Crushing the cylindrical catalyst, sieving to obtain 0.5 g of catalyst particles of 20-40 meshes, placing the catalyst particles of example 1 into a continuous flow fixed bed reactor, and making the reaction gas composition be 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature is 300-500 ℃ and the N is catalytically decomposed 2 The conversion of O is shown in Table 2.
Application example 2
Crushing the cylindrical catalyst, sieving to obtain 0.5 g of catalyst particles of example 2 with 20-40 meshes, and placingIn the continuous flow fixed bed reactor, the composition of the reaction gas was 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature is 300-500 ℃ and the N is catalytically decomposed 2 The conversion of O is shown in Table 2.
Application example 3
Crushing the cylindrical catalyst, sieving to obtain 0.5 g of catalyst particles of 20-40 meshes, placing the catalyst particles of example 3 into a continuous flow fixed bed reactor, and making the reaction gas composition be 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature is 300-500 ℃ and the N is catalytically decomposed 2 The conversion of O is shown in Table 2.
Comparative application example 1
0.5 g of the nanocomposite of comparative example 1 was placed in a continuous flow fixed bed reactor with a reaction gas composition of 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature is 300-500 ℃ and the N is catalytically decomposed 2 The conversion of O is shown in Table 2.
Comparative application example 2
0.5 g of the nanocomposite of comparative example 2 was placed as catalyst in a continuous flow fixed bed reactor with a reaction gas composition of 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature is 300-500 ℃ and the N is catalytically decomposed 2 The conversion of O is shown in Table 2.
Comparative application example 3
Crushing the cylindrical catalyst, sieving to obtain 0.5 g of catalyst particles of comparative example 3 with 20-40 meshes, placing the catalyst particles in a continuous flow fixed bed reactor, and making the reaction gas composition be 38.0% N 2 O, nitrogen was used as an equilibrium gas, and the flow rate of the reaction gas was 15ml/min. The activity evaluation temperature is 300-500 ℃ and the N is catalytically decomposed 2 The conversion of O is shown in Table 2.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2 above, the shaped catalyst prepared by the method of the present invention not only has higher mechanical strength, but also has improved N by doping with alkali metal and/or alkaline earth metal 2 The O catalytic decomposition performance can meet the requirements of industrial application and can efficiently eliminate N at 360-420 DEG C 2 O. When the formed catalyst provided by the invention is applied to the waste gas treatment in the adipic acid production process, the reaction temperature can be greatly reduced, the energy consumption is reduced, the activity is high, and the stability is good.
For shaped catalysts of particulate active components, the activity of the shaped catalyst is generally reduced compared to the same mass of active component while increasing the mechanical strength of the catalyst; however, the catalytic activity of the shaped catalysts according to the invention can be maintained or slightly increased.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (11)
1. A method for catalyzing nitrous oxide decomposition is characterized by comprising the steps of adopting a catalyst to contact nitrous oxide for catalytic decomposition reaction to generate nitrogen and oxygen, wherein the catalyst comprises a carrier, an active component and an auxiliary agent which are loaded on the carrier,
the active component is a carbon-coated nickel nanocomposite, the nanocomposite comprises a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer, and the inner core is nickel nano particles;
the auxiliary agent comprises a second metal oxide, wherein the second metal oxide is an oxide of alkali metal and/or alkaline earth metal, and the molar ratio of the second metal to nickel is 0.01-0.3;
in the catalytic decomposition reaction, the reaction temperature is 300-420 ℃, the reaction space velocity is 500-3000 ml of reaction gas/(hour gram of catalyst), and the volume concentration of nitrous oxide is 30% -40%.
2. The method of claim 1, wherein the nickel is present in an amount of 16% to 76%, the support is present in an amount of 10% to 60%, and the carbon is present in an amount of 6% to 54% based on the weight of the catalyst.
3. The method according to claim 1, wherein the catalyst is prepared by the steps of:
providing a carbon-coated nickel nanocomposite as raw powder, preparing a second metal salt solution, uniformly mixing the carbon-coated nickel nanocomposite with the second metal salt solution, and stirring to obtain a solid-liquid mixture; drying and first roasting the solid-liquid mixture to obtain solid powder; adding a binder into the solid powder, and uniformly mixing to obtain a wet dough;
the wet dough is subjected to forming treatment, the formed body is dried, and then the second roasting treatment is carried out in inert atmosphere, so that the catalyst of carbon-coated nickel is obtained;
wherein the second metal salt solution is selected from alkali metal salt solutions and/or alkaline earth metal salt solutions.
4. A method according to claim 3, wherein the first firing process comprises: heating the dried solid-liquid mixture to 200-500 ℃ at a heating rate of 1-20 ℃/min, and keeping the constant temperature for 0.5-10 h; the second firing treatment includes: heating the product after the molding treatment to 400-800 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature for 1-10 h.
5. A method according to claim 3, wherein the binder is an aluminium sol, a silica sol or a silica alumina sol.
6. A method according to claim 3, wherein the binder is made from pseudo-boehmite and a peptizing agent selected from one or more of aqueous nitric acid, aqueous hydrochloric acid and aqueous citric acid.
7. The method of claim 6, wherein the binder further comprises a lubricant selected from one or more of sesbania powder, citric acid, starch, and carboxymethyl cellulose; the mass of the lubricant is 1-6% of the mass of the raw powder.
8. A method according to claim 3, wherein the mass ratio of liquid to solid in the wet mass is 0.8 to 1.5:1, the raw powder accounts for 20-80% of the mass of the solid in the wet dough.
9. A method according to claim 3, wherein the drying temperature is 20 ℃ to 100 ℃, the drying time is 3 hours to 24 hours, and the drying atmosphere is an inert atmosphere or an air atmosphere.
10. A method according to claim 3, wherein the shaping treatment is selected from one or more of extrusion, rolling and pelletization.
11. A method according to claim 3, wherein the carbon-coated nickel nanocomposite comprises a core-shell structure having a shell layer and an inner core, the shell layer being a graphitized carbon layer and the inner core being nickel nanoparticles, the carbon content being 15 wt.% to 60 wt.% and the nickel content being 40 wt.% to 85 wt.% based on the weight of the carbon-coated nickel nanocomposite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110312087.6A CN115121110B (en) | 2021-03-24 | 2021-03-24 | Method for catalyzing decomposition of nitrous oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110312087.6A CN115121110B (en) | 2021-03-24 | 2021-03-24 | Method for catalyzing decomposition of nitrous oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115121110A CN115121110A (en) | 2022-09-30 |
| CN115121110B true CN115121110B (en) | 2023-08-08 |
Family
ID=83375073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110312087.6A Active CN115121110B (en) | 2021-03-24 | 2021-03-24 | Method for catalyzing decomposition of nitrous oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115121110B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117117516B (en) * | 2023-06-02 | 2024-02-20 | 太仓碧奇新材料研发有限公司 | Preparation method of organic/inorganic hybrid sub-terahertz wave-absorbing film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0643988A1 (en) * | 1993-09-16 | 1995-03-22 | Rohm And Haas Company | Process for decomposing nitrogen oxides |
| AU4428296A (en) * | 1995-01-25 | 1996-08-14 | Gaz Metropolitain And Company, Limited Partnership | Selective catalytic reduction of nitrogen oxides |
| CN107670669A (en) * | 2017-11-06 | 2018-02-09 | 方文成 | A kind of nitrous oxide decomposes catalysis material and preparation method thereof |
| CN108358249A (en) * | 2018-02-09 | 2018-08-03 | 中南大学 | A kind of preparation method of anode material for lithium-ion batteries nickel molybdate |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU191810B (en) * | 1981-09-21 | 1987-04-28 | Mta Mueszaki Kemiai Kutato Int | Bifunctional catalyzer containing gamma-alumina and nickelic oxide for autothermic splitting fuels |
| US6379640B1 (en) * | 1999-03-05 | 2002-04-30 | E. I. Du Pont De Nemours And Company | Process for the decomposition of nitrous oxide |
| DE10020100A1 (en) * | 2000-04-22 | 2001-10-31 | Dmc2 Degussa Metals Catalysts | Process and catalyst for the reduction of nitrogen oxides |
| JP4573320B2 (en) * | 2000-09-08 | 2010-11-04 | 昭和電工株式会社 | Nitrous oxide decomposition catalyst, production method thereof, and decomposition method of nitrous oxide |
| CN105381801A (en) * | 2015-11-12 | 2016-03-09 | 开滦（集团）有限责任公司 | Catalyst capable of directly catalytically decomposing N2O |
| CN108856706B (en) * | 2017-05-10 | 2020-03-24 | 中国石油化工股份有限公司 | Carbon-coated nickel-aluminum composite material and preparation method and application thereof |
| CN107398283B (en) * | 2017-06-23 | 2021-02-26 | 清华大学 | Catalyst metal heating surface for reducing NOx content in flue gas and preparation method thereof |
| CN109305918B (en) * | 2017-07-28 | 2022-10-21 | 中国石油化工股份有限公司 | Synthesis method of halogenated aniline |
| CN107876078A (en) * | 2017-11-06 | 2018-04-06 | 西南石油大学 | A kind of graphene, TiO2Catalysis material of carbonitride load nickel foam and preparation method and application |
| CN108479218B (en) * | 2018-04-19 | 2020-05-12 | 南京信息工程大学 | Filter bag cage rib with denitration function and preparation method thereof |
| CN111468154A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Carbon-coated transition metal nanocomposite and preparation method and application thereof |
-
2021
- 2021-03-24 CN CN202110312087.6A patent/CN115121110B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0643988A1 (en) * | 1993-09-16 | 1995-03-22 | Rohm And Haas Company | Process for decomposing nitrogen oxides |
| AU4428296A (en) * | 1995-01-25 | 1996-08-14 | Gaz Metropolitain And Company, Limited Partnership | Selective catalytic reduction of nitrogen oxides |
| EP0805712A1 (en) * | 1995-01-25 | 1997-11-12 | Gaz Métropolitain and Company, Limited Partnership | Selective catalytic reduction of nitrogen oxides |
| CN107670669A (en) * | 2017-11-06 | 2018-02-09 | 方文成 | A kind of nitrous oxide decomposes catalysis material and preparation method thereof |
| CN108358249A (en) * | 2018-02-09 | 2018-08-03 | 中南大学 | A kind of preparation method of anode material for lithium-ion batteries nickel molybdate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115121110A (en) | 2022-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109305875B (en) | Synthesis method of naphthenic compound | |
| Chen et al. | Multicomponent metal oxides derived from Mn-BTC anchoring with metal acetylacetonate complexes as excellent catalysts for VOCs and CO oxidation | |
| CN108421545B (en) | Application of manganese dioxide composite material | |
| US20130252806A1 (en) | Ag/MnyOx/C CATALYST, PREPARATION AND APPLICATION THEREOF | |
| Wang et al. | Facile solid-state synthesis of highly dispersed Cu nanospheres anchored on coal-based activated carbons as an efficient heterogeneous catalyst for the reduction of 4-nitrophenol | |
| TW202120177A (en) | Carbon-coated nickel oxide nanocomposite material, preparation method therefor and use thereof | |
| CN113751004B (en) | Catalyst of carbon-coated transition metal oxide, preparation method and application thereof | |
| CN115121110B (en) | Method for catalyzing decomposition of nitrous oxide | |
| Gao et al. | Excellent performance and outstanding resistance to SO2 and H2O for formaldehyde abatement over CoMn oxides boosted dual-precursor hierarchical porous biochars derived from liquidambar and orange peel | |
| CN113751007B (en) | Catalyst of carbon-coated nickel oxide, preparation method and application thereof | |
| CN113751005B (en) | Catalyst of carbon-coated transition metal oxide, preparation method and application thereof | |
| Fu et al. | Oxidative decomposition of chlorobenzene on MnaVOX catalysts: The critical roles of oxygen vacancies and hollow structure | |
| CN113750781B (en) | Method for catalytic decomposition of nitrous oxide | |
| CN113750991B (en) | Catalyst of carbon-coated nickel oxide, preparation method and application thereof | |
| CN113751042B (en) | Carbon-coated nickel oxide nano composite material and preparation method and application thereof | |
| CN113751006B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN113751041B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN113751008B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN113617357A (en) | Preparation method and application of nickel oxide catalyst for removing VOCs (volatile organic compounds) by coupling low-temperature plasma | |
| Zhuge et al. | Morphologically controllable spinel catalysts CuCo2O4 for boosting catalytic oxidation of toluene | |
| CN112755994A (en) | Carbon-coated nickel-aluminum nano composite material and preparation method and application thereof | |
| CN112755993B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN113751003B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN117138784B (en) | High-loading high-dispersion Cu-based catalyst and synthesis method and application thereof | |
| EP4049752A1 (en) | Carbon-coated nickel-aluminum nanocomposite, preparation method therefor and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |