CN115121110A - Method for catalyzing decomposition of nitrous oxide - Google Patents
Method for catalyzing decomposition of nitrous oxide Download PDFInfo
- Publication number
- CN115121110A CN115121110A CN202110312087.6A CN202110312087A CN115121110A CN 115121110 A CN115121110 A CN 115121110A CN 202110312087 A CN202110312087 A CN 202110312087A CN 115121110 A CN115121110 A CN 115121110A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon
- nickel
- mass
- metal
- 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.)
- Granted
Links
Images
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)
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The application relates to a method for catalyzing decomposition of nitrous oxide, which comprises the steps of contacting a catalyst with nitrous oxide to carry out catalytic decomposition reaction, wherein the catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier, the active component is a carbon-coated nickel nanocomposite material, the nanocomposite material 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, 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 catalytic decomposition of 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 nickel nanoparticles are receiving much attention due to their excellent optical, electrical, and magnetic properties. However, the metal nickel nanoparticles have high activity, are easy to agglomerate or be oxidized or even burn in the air, and greatly influence the performance and application of the materials. Meanwhile, as a non-metallic 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 nano particles of the active metal are coated by the carbon material, so that the conductivity and the stability of the nano material can be effectively improved, and the nano material has the effect of a limited domain and is not easy to oxidize and agglomerate. In recent years, nanocarbon-coated metal composite materials have become a focus of attention. The material takes single-layer to multiple-layer bent graphitized carbon layers as metal nano particles with shells tightly wrapping the inner core, and the nano particles are isolated from the outside, so that 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, the Global Warming Potential (GWP) of which is CO 2 310 times of, CH 4 21 times of the total weight of the composition; furthermore, N 2 O has an average life in the atmosphere of about 150 years and is also NO in the stratosphere x The main source of the compound can not only seriously damage the ozone layer, but also has strong greenhouse effect.
The domestic production of adipic acid mainly adopts a cyclohexanol nitric acid oxidation method, and the cyclohexanol is subjected to nitric acid oxidation to produce adipic acid, and the method is mature in technology, high in product yield and purity, but large in nitric acid consumption, and capable of producing a large amount of N in the reaction process 2 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 a nitric acid oxidation method of cyclohexanol 2 The annual emission of O can reach 4.5 ten thousand tons. Therefore, the tail gas of the adipic acid device is purified, and N is effectively controlled and eliminated 2 O has become a research hotspot in the field of environmental catalysis at present.
By direct catalytic decomposition of N 2 O is decomposed into nitrogen and oxygen to eliminate N 2 O is the most efficient and clean technique. Among them, the catalyst is the core of the direct catalytic decomposition method. Decomposition of N reported in the present study 2 The catalyst of O mainly comprises noble metal catalyst, ion-exchanged molecular sieve catalyst and transition metal oxide catalyst. Noble metal catalysts (e.g., Rh and Ru) vs. N 2 The O catalytic decomposition has higher low-temperature catalytic activity (within the range of 250-350 ℃) and can efficiently decompose N 2 O), but the expensive price limits the large-scale application of noble metal catalysts. The price of molecular sieve catalyst and transition metal oxide catalyst is obviously lower than that of noble metal, but at present, the two catalysts are used for N 2 The activity of O catalytic decomposition is low, and the temperature range of efficient decomposition is 450-550 ℃. Therefore, the development of a new non-noble metal, low cost and efficient new material catalyst couple N 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 background understanding 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
One of the main objects of the present invention is to overcome at least one of the drawbacks of the prior art mentioned above, and to provide a method for catalytically decomposing nitrous oxide, wherein a catalyst used in the method comprises carbon-coated nickel doped with alkali metal and/or alkaline earth metal, and a nanocomposite material of carbon-coated nickel is used as a raw powder, and is processed by a specific process, such that a catalyst having excellent catalytic activity and good mechanical properties can be obtained, and industrial application requirements can be satisfied, and particularly, after being doped with alkali metal and/or alkaline earth metal, the catalyst has a superior effect on catalytically decomposing nitrous oxide, and has a good industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for catalyzing nitrous oxide decomposition comprises the step of contacting a catalyst with nitrous oxide to perform catalytic decomposition reaction to generate nitrogen and oxygen, wherein the catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier,
the active component is a carbon-coated nickel nanocomposite material, the nanocomposite material 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, 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 content is 16% to 76%, the support content is 10% to 60%, and the carbon content is 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 nano composite material as raw powder, preparing a second metal salt solution, uniformly mixing the carbon-coated nickel nano composite material and 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 material mass;
forming the wet dough, drying the formed body, and performing second roasting treatment in an inert atmosphere to obtain a carbon-coated nickel catalyst;
wherein the second metal salt solution is selected from an alkali metal salt solution and/or an alkaline earth metal salt solution.
In one embodiment, the first firing treatment comprises: heating the dried solid-liquid mixture to 200-500 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature constant for 0.5-10 h; the second firing treatment includes: heating the formed product to 400-800 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature constant 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 prepared from pseudoboehmite 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 liquid-solid mass ratio in the wet mass is 0.8 to 1.5: 1, the raw powder accounts for 20-80% of the mass of solids in the wet dough.
In one embodiment, the drying temperature is 20 ℃ to 100 ℃, the drying time is 3h to 24h, and the drying atmosphere is an inert atmosphere or an air atmosphere.
In one embodiment, the shaping process is selected from one or more of extruding, rolling and pelletizing.
In one embodiment, the carbon-coated nickel nanocomposite comprises a core-shell structure having a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer, the inner core is a nickel nanoparticle, and the carbon content is 15 wt% to 60 wt% and the nickel content is 40 wt% to 85 wt% 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 catalyst), and the volume concentration of the nitrous oxide is 30-40%.
According to the technical scheme, the invention has the beneficial effects that:
compared with the prior catalyst, the catalyst must remove N in industrial waste gas 2 The catalyst of the method can directly catalyze and decompose the high-concentration nitrous oxide waste gas generated in industrial production at lower temperature, the decomposition rate can reach more than 99 percent, and the catalyst has important significance for protecting the environment and reducing the air pollution and has good industrial application prospect. The catalyst used in the method of the invention is prepared by taking the carbon-coated nickel nano composite material as raw powder, so as to obtain the carbon-coated nickel catalyst with unique structure and composition, and in addition, the catalyst is doped with a second metal, namely alkali metal and/or alkaline earth metal, which catalyzes N 2 The catalytic activity is further improved in the case of O decomposition reaction.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is an X-ray diffraction pattern of the product obtained in step (2) of example 1;
FIG. 2 is a transmission electron microscope photograph of a product obtained in step (2) of example 1;
FIG. 3 is an X-ray diffraction pattern of the product obtained in step (2) of example 2;
FIG. 4 is a transmission electron microscope photograph of the product obtained in step (2) of example 2.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to be limiting. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The application provides a method for catalyzing nitrous oxide decomposition, which comprises the steps of contacting a catalyst with nitrous oxide to carry out catalytic decomposition reaction to generate nitrogen and oxygen, wherein the catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier,
the active component is a carbon-coated nickel nanocomposite material, the nanocomposite material comprises a core-shell structure with a shell layer and a core, the shell layer is a graphitized carbon layer, and the core is nickel nanoparticles;
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 nickel is 0.01-0.3.
The carbon-coated nickel catalyst used in the method comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier,
the active component is a carbon-coated nickel nanocomposite material, the nanocomposite material 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, 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 content is 16% to 76%, the support content is 10% to 60%, and the carbon content is 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 certain pore structure, and in some embodiments, the specific surface area of the catalyst of the present invention is 150m 2 /g～240m 2 Per g, pore volume 0.30cm 3 /g～0.50cm 3 (iv) g, the crushing strength is 50N/cm to 120N/cm. In one embodiment, the catalyst is usedThe amount of carrier may be from 10% to 50%, 10% to 40%, 10% to 35%, or 10% to 30% by weight.
The catalyst of the application is further improved by the carbon-coated nickel nano composite material, and the additive is added, so that the performance of the catalyst can be further improved.
In the application, the carbon-coated nickel nanocomposite material as the active component of the catalyst comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer, the inner core is nickel nanoparticles, and the carbon content is 15 wt% -60 wt% and the nickel content is 40 wt% -85 wt% based on the weight of the carbon-coated nickel nanocomposite material. In one embodiment, the particle size of the carbon-coated nickel nanocomposite material can be 1 to 100nm, preferably 2 to 40 nm.
The carbon-coated nickel nanocomposite can be purchased from the market, and can also be prepared by adopting the following method:
putting a nickel source and carboxylic acid into a solvent to be mixed 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 refers to a nickel-containing water-soluble mixture obtained by dissolving a nickel source and a carboxylic acid in a solvent such as water, ethanol, etc. to form a homogeneous solution and then directly evaporating the solvent. The foregoing temperature and process of evaporating the solvent may be by any available prior art, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven.
In some embodiments, the nickel source is selected from one or more of soluble organic acid salts, basic carbonates, hydroxides and oxides 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 mentioned above, which can be any organic compound that can supplement the carbon source required in the product without containing other doping atoms, can also be added to form a homogeneous solution. Organic compounds having no volatility such as organic polyols, lactic acid and the like are preferable. In some embodiments, the mass ratio of the nickel source, the carboxylic acid, and the other organic compound is 1:0.1 to 10:0 to 10, preferably 1:0.5 to 5:0 to 5, and more preferably 1:0.8 to 3:0 to 3.
In some embodiments, pyrolyzing 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 ℃/min to 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, and the like; the temperature of the constant temperature section is 400-800 ℃, preferably 500-700 ℃, such as 500 ℃, 550 ℃, 570 ℃, 610 ℃, 660 ℃, 680 ℃ and the like; the constant temperature time is 20min to 600min, preferably 30min to 300min, such as 30min, 45min, 55min, 70min, 86min, 97min, 100min, 180min, 270min, 300min and the like; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of an 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, other methods can be adopted to prepare the carbon-coated nickel nanocomposite, but the invention is not limited thereto.
In some embodiments, the present invention further comprises acid washing the carbon-coated nickel nanocomposite obtained after pyrolysis as described above. The nano composite material is a nano composite material formed by coating a graphitized carbon layer with nickel. The graphitized carbon layer is a carbon structure with a layered structure, but not an amorphous structure, which can be obviously observed under a high-resolution transmission electron microscope, and the interlayer distance is about 0.34 nm. The nano composite material with the graphitized carbon layer coated with the nickel is a composite material consisting of nickel nano particles tightly coated (not contacted with the outside) by the graphitized carbon layer, nickel nano particles which can be contacted with the outside and are confined and a carbon material with a mesoporous structure. After the acid washing treatment, nickel in the composite material has certain loss, and can be represented by the acid washing loss rate. That is, the "pickling loss ratio" refers to the loss ratio of nickel after pickling of the prepared carbon-coated nickel nanocomposite product. Which reflects how tightly the graphitized carbon layer coats the nickel. If the graphitized carbon layer does not coat the nickel tightly, the nickel of the core will be dissolved by the acid and lost after the acid treatment. The larger the acid washing loss rate, the lower the degree of tightness of the nickel coating by the graphitized carbon layer, and the smaller the acid washing loss rate, the higher the degree of tightness of the nickel coating by the graphitized carbon layer.
Generally, the specific conditions of the pickling treatment are: adding 1g of sample into 20mL of sulfuric acid aqueous solution (1mol/L), treating the sample at 90 ℃ for 8h, then washing the sample to be neutral by using deionized water, weighing and analyzing the sample after drying, and calculating the pickling loss rate according to the following formula.
The calculation formula is as follows: the acid pickling loss rate is [1- (mass fraction of nickel in the composite material after acid pickling × mass of the composite material after acid pickling) ÷ (mass fraction of nickel in the composite material to be treated × mass of the composite material to be treated) ] × 100%. In some embodiments, the composite material generally has an acid loss rate of 60% or less, can be 40% or less, can be 30% or less, can be 20% or less, and can be 10% or less.
In some common chemical processes, such as fixed bed process, not only certain activity and selectivity of the catalyst are required, but also certain requirements on properties such as particle size and mechanical strength are required. The catalyst particles are too small or are broken and pulverized due to insufficient strength, so that the catalyst is easily carried and lost or blocks the device in the reaction process, the pressure drop of a catalyst bed is greatly increased, and even the device is forced to stop. The carbon-coated nano material has small particles, is powdery and has poor self-forming performance, and if the carbon-coated nano material is applied to the processes, the carbon-coated nano material needs to be formed so as to meet the industrial reaction requirements of compressive strength, pressure drop after filling, stability and the like. The molding treatment is a process of aggregating raw materials such as catalyst raw powder and molding aid to prepare solid particles having a certain size, shape and mechanical strength. The forming process has 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 maintain the catalytic performance of the carbon-coated nano material as much as possible is a research focus of a carbon-coated nano material forming method.
For the catalyst 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 nano composite material as raw powder, preparing a second metal salt solution, uniformly mixing the carbon-coated nickel nano composite material and 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 mass;
forming the wet dough, drying the formed body, and performing second roasting treatment in an inert atmosphere to obtain a carbon-coated nickel catalyst;
wherein the second metal salt solution is selected from an alkali metal salt solution and/or an alkaline earth metal salt solution.
Specifically, in the method, a carbon-coated nickel nano composite material is used as raw powder, a second metal salt solution is prepared, the carbon-coated nickel nano composite material 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 first roasted to obtain solid powder, and the second metal salt is doped into the raw powder through impregnation in the process; and adding a binder into the solid powder, and uniformly mixing to obtain a wet mass.
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, and preferably, a potassium nitrate solution or a potassium carbonate solution. In the process, the addition amount of the second metal salt solution can be controlled so that the molar ratio of the second metal to the nickel is 0.01-0.3, or 0.01-0.2.
In one embodiment, the drying temperature of the above process is 20 ℃ to 100 ℃, the drying time is 3h to 24h, and the drying atmosphere is an inert atmosphere or an air atmosphere.
In one embodiment, the first firing treatment of the above process comprises: heating the dried solid-liquid mixture to 200-500 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature constant 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 pseudoboehmite and a peptizing agent selected from one or more of an aqueous nitric acid solution, an aqueous hydrochloric acid solution and an aqueous citric acid solution. 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 liquid-solid mass ratio in the wet mass may be 0.8 to 1.5: 1, the raw powder accounts for 20-80% of the mass of solids in the wet dough. In some embodiments, the liquid-solid mass ratio in the wet mass is 0.8 to 1.5, such as 0.8, 0.9, 1, 1.2, etc., preferably 0.85 to 1. The raw meal comprises 20% to 80% of the mass of solids in the wet mass, for example 20%, 25%, 31%, 47%, 56%, 60%, 75%, etc. The binder accounts for 20-80% of the mass of solids in the wet mass, such as 22%, 36%, 41%, 47%, 55%, 67%, 80%, etc.; the mass of the lubricant is 1% to 6% of the mass of the raw powder, for example, 1%, 2%, 4%, 5%, 6%, etc., preferably 2% to 3%.
After obtaining a wet dough of a desired composition, the wet dough is subjected to a forming process, wherein the forming process is one or more of extruding, rolling and granulating, and the invention is not limited thereto.
After the molding treatment, the molded article obtained is dried at a temperature of 20 to 100 ℃ such as 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 65 ℃, 70 ℃, 72 ℃, 82 ℃, 88 ℃ or the like. The drying time is 3h to 24h, for example, 3h, 4h, 6h, 7h, 10h, 12h, 13h, 17h, 20h, 24h and the like. The drying atmosphere is an inert atmosphere or an air atmosphere.
After the drying treatment, the resulting product is further subjected to a second calcination treatment under an inert atmosphere, which is nitrogen, inert gas in the usual sense, or other non-oxidizing gas. In one embodiment, the second firing treatment comprises: heating the formed product to 400-800 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature constant for 1-10 h.
Thus, the carbon-coated nickel catalyst of the present application can be obtained. The catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier, wherein the active component is a carbon-coated nickel nanocomposite material, the nanocomposite material comprises a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer, the inner core is nickel nanoparticles, 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 nickel is 0.01-0.3. According to the invention, the aforementioned support may be alumina and/or silica. The catalyst has a certain pore structure, and in some embodiments, the specific surface area of the catalyst of the present invention is 150m 2 /g～240m 2 Per g, pore volume 0.30cm 3 /g～0.50cm 3 (iv) g, the crushing strength is 50N/cm to 120N/cm.
It should be noted that, for the present invention, the specific surface area and pore volume of the catalyst obtained by different binders (such as alumina sol, silica sol, pseudo-boehmite, etc.) and different forming conditions (such as pressure) and forming modes (extruding, rolling, granulating) are greatly different, so the specific surface area, pore volume and crushing strength ranges can also be adjusted according to the actual operating conditions and the requirements for the catalyst strength, etc., and the present invention is not limited thereto.
The catalyst has good catalytic activity, particularly the activity of catalyzing the decomposition of the nitrous oxide, so the application provides a method for catalyzing the decomposition of the nitrous oxide by using the catalyst, and specifically, a gas containing the nitrous oxide is introduced into a reactor provided with the catalyst to carry out catalytic decomposition reaction to generate nitrogen and oxygen.
In some embodiments, the temperature of the catalytic decomposition reaction is from 300 ℃ to 420 ℃, preferably from 360 ℃ to 420 ℃. The space velocity of the catalytic decomposition reaction is 500-3000 ml of reaction gas/(h.g of catalyst). The high reaction space velocity allowed by the invention shows that the catalyst of the invention has high activity and large device processing capacity when the reaction is applied.
According to the invention, as mentioned above, the currently reported decomposition N 2 The catalyst of O mainly comprises noble metal catalyst, ion-exchanged molecular sieve catalyst and transition metal oxide catalyst. Although the decomposition temperature of the noble metal catalyst is low, the expensive price of the noble metal catalyst is not suitable for large-scale industrial production; the high-efficiency decomposition temperature of other molecular sieve catalysts and transition metal oxide catalysts 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 catalytic activity stability in the reaction. In addition, when the existing catalyst is used for catalyzing and decomposing the nitrous oxide, the high-concentration nitrous oxide obtained by industrial production generally needs to be diluted to be about 0.5-2 percent, and the catalyst can be directly decomposed to achieve a high decomposition rate without being diluted. Namely, the nitrous oxide can be subjected to catalytic decomposition reaction when the volume concentration is 36-40%, and the decomposition rate can reach more than 99%, so that the industrial cost is greatly reduced, and the method has a good industrial application prospect.
Accordingly, the present application relates to a method for catalyzing the decomposition of nitrous oxide comprising contacting nitrous oxide with a catalyst comprising nickel coated with carbon according to 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 catalyst), and the volume concentration of the nitrous oxide is 30-40%.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, all reagents used in the invention are analytically pure.
The analysis of carbon (C) element is carried out on an Elementar Micro Cube element analyzer which is mainly used for analyzing four elements of carbon (C), hydrogen (H), oxygen (O) and nitrogen (N), and the specific operation method and conditions are as follows: weighing 1-2 mg of a sample in a tin cup, placing the sample in an automatic sample feeding disc, feeding the sample into a combustion tube through a ball valve for combustion, wherein the combustion temperature is 1000 ℃ (the atmosphere interference during sample feeding is removed, helium is adopted for blowing), and then reducing the combusted gas by using reduced copper 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 oxygen element is analyzed by converting oxygen in a sample into CO under the action of a carbon catalyst by utilizing pyrolysis, and then detecting the CO by adopting TCD. Since the raw powder carbon-coated nickel of the present invention contains only carbon, hydrogen, oxygen and metallic nickel, the total content of metallic nickel can be known from the contents of carbon, hydrogen and oxygen elements.
The ratio between the different metal oxides in the catalyst was determined by X-ray fluorescence Spectroscopy (XRF), and the content of the different metal oxides in the composite was calculated from the known carbon content. The X-ray fluorescence spectrum analyzer (XRF) adopted by the invention is a Rigaku 3013X-ray fluorescence spectrometer, and the X-ray fluorescence spectrum analysis and test conditions are as follows: the scanning time was 100s and the atmosphere was air.
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100(HRTEM) (Nippon electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV.
The XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu, Japan), and the XRD test conditions are as follows: the Cu target was irradiated with K α rays (wavelength λ is 0.154nm), tube voltage was 40kV, tube current was 200mA, and scanning speed was 10 ° (2 θ)/min.
The pore structure property of the material is detected by a BET test method. Specifically, a Quantachrome AS-6B type analyzer is adopted for determination, and the specific surface area, pore volume and average pore diameter of the catalyst are the most probable pore diameters.
The crushing strength of the invention refers to the pressure when each catalyst is crushed, the strength is measured by adopting an ZQJ-III type intelligent particle strength tester of Dalian intelligent tester factory, 20 catalysts in the same batch are randomly extracted, and the ratio of the particle size to the length is 1: 1-1.5, performing a crush strength test, removing the maximum value and the minimum value, taking the arithmetic mean value as a Newton value F (N) when single particles are crushed, and calculating the radial crush strength sigma (N/cm) of the single particles according to a formula sigma F/L, wherein L is the length (cm) of the single particle catalyst.
Example 1
This example illustrates the preparation of a catalyst according to the invention
(1) Weighing 10g of nickel carbonate and 10g of citric acid, adding the nickel carbonate and the citric acid into a beaker containing 100mL of deionized water, stirring the mixture at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the homogeneous solution to dryness to obtain a solid precursor.
(2) And (2) 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, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite. Element analysis shows that the carbon-coated nickel nanocomposite comprises the following elements in percentage by mass: 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 the nanocomposite of the material, which shows that the nanocomposite is a carbon-coated nickel nanocomposite, and the outer layer of the nickel nanoparticle is coated with a graphitized carbon layer, which has a core-shell structure.
(3) Adding K 2 CO 3 Stirring the aqueous solution with the molar ratio of potassium to nickel of 0.01 for 2 hours, placing the aqueous solution in an oven at 80 ℃ and drying the aqueous solution for 12 hours.
(4) And (3) uniformly mixing the pseudoboehmite with the mass fraction of 50% of the total powder mass and the product obtained in the step (3) at room temperature, adding sesbania powder with the mass fraction of 1.5% of the raw powder mass, uniformly mixing, preparing 1mol/L nitric acid aqueous solution from nitric acid with the mass fraction of 2.5% of the pseudoboehmite mass, dropwise adding, and continuously stirring until the materials are uniformly mixed to obtain a wet material mass.
(5) Extruding the wet material mass on an F-26 double-screw extruder (manufactured by general science and technology industries of southern China university) by using a phi 3mm circular orifice plate to form strips, obtaining solid cylindrical strips, cutting the solid cylindrical strips into particles with the length of 3-4 mm, placing the particles in an oven, drying the particles for 24 hours at 40 ℃, then placing the particles in a tube furnace, introducing nitrogen, heating the particles to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 4 hours, stopping heating, cooling the particles to room temperature under the nitrogen atmosphere to obtain a cylindrical strip catalyst, and measuring the crushing strength, specific surface and pore volume of the cylindrical strip catalyst, wherein the results are shown in table 1. XRF elemental analysis showed that the shaped catalyst contained 16.82 wt% carbon, 0.41 wt% potassium oxide, 46.63 wt% nickel and 36.14 wt% alumina.
The specific surface, pore volume, pore diameter and crush strength of the catalyst are shown in Table 1.
Example 2
(1) Weighing 10g of nickel acetate and 10g of citric acid, adding the nickel acetate and the citric acid into a beaker containing 100mL of deionized water, stirring the mixture at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the solution to dryness to obtain a solid precursor.
(2) And (2) 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, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite. Element analysis shows that the carbon-coated nickel nanocomposite comprises the following elements in percentage by mass: 24.29 percent of carbon, 0.47 percent of hydrogen, 0.96 percent of oxygen and 74.28 percent 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 the nanocomposite of the material, which shows that the nanocomposite is a carbon-coated nickel nanocomposite, and the outer layer of the nickel nanoparticle is coated with a graphitized carbon layer, which has a core-shell structure.
(3) Adding K 2 CO 3 The aqueous solution, wherein the molar ratio of potassium to nickel is 0.1, is stirred for 2 hours, placed in an oven at 80 ℃ and dried for 12 hours.
(4) Uniformly mixing the pseudoboehmite with the mass fraction accounting for 25% of the total powder mass and the product obtained in the step (3) at room temperature, adding sesbania powder with the mass fraction accounting for 1.5% of the raw powder mass, uniformly mixing, preparing nitric acid with the mass fraction accounting for 2.5% of the pseudoboehmite mass into a 1mol/L nitric acid aqueous solution, dropwise adding, and continuously stirring until the materials are uniformly mixed; a wet mass is obtained.
(5) Extruding the wet material mass on an F-26 double-screw extruder (manufactured by general science and technology industries of southern China university) by using a phi 3mm circular orifice plate to form strips, obtaining solid cylindrical strips, cutting the solid cylindrical strips into particles with the length of 3-4 mm, placing the particles in an oven, drying the particles for 24 hours at 40 ℃, then placing the particles in a tube furnace, introducing nitrogen, heating the particles to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 4 hours, stopping heating, cooling the particles to room temperature under the nitrogen atmosphere to obtain a cylindrical strip catalyst, and measuring the crushing strength, specific surface and pore volume of the cylindrical strip catalyst, wherein the results are shown in table 1. XRF, elemental analysis showed that the shaped catalyst contained 19.34 wt% carbon, 4.13 wt% potassium oxide, 58.91 wt% nickel, and 17.62 wt% alumina.
The specific surface, pore volume and 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, wherein the molar ratio of potassium to nickel is 0.1, is stirred for 2 hours, placed in an oven at 80 ℃ and dried for 12 hours.
(2) Uniformly mixing pseudo-boehmite with the mass fraction of 25% of the total powder mass and the carbon-coated nickel nano composite material obtained in the step (1) at room temperature, adding sesbania powder with the mass fraction of 1.5% of the original powder mass, uniformly mixing, preparing nitric acid with the mass fraction of 2.5% of the pseudo-boehmite mass into 1mol/L nitric acid aqueous solution, dropwise adding, and continuously stirring until the materials are uniformly mixed to obtain a wet material mass;
(3) extruding the wet material mass on an F-26 double-screw extruder (manufactured by general science and technology industries of southern China university) by using a phi 3mm circular orifice plate to form strips, obtaining solid cylindrical strips, cutting the solid cylindrical strips into particles with the length of 3-4 mm, placing the particles in an oven, drying the particles for 24 hours at 40 ℃, then placing the particles in a tube furnace, introducing nitrogen, heating the particles to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 4 hours, stopping heating, cooling the particles to room temperature under the nitrogen atmosphere to obtain a cylindrical strip catalyst, and measuring the crushing strength, specific surface and pore volume of the cylindrical strip catalyst, wherein the results are shown in table 1. XRF elemental analysis showed that the shaped catalyst contained 20.63 wt% carbon, 4.24 wt% potassium oxide, 58.02 wt% nickel and 17.11 wt% alumina.
The specific surface, pore volume and 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) Taking the carbon-coated nickel nano composite material obtained in the step (2) in the embodiment 2 as raw powder, uniformly mixing the pseudo-boehmite with the raw powder at room temperature, wherein the mass fraction of the pseudo-boehmite accounts for 25% of the total powder mass, adding sesbania powder with the mass fraction of 1.5% of the raw powder mass, uniformly mixing, preparing nitric acid with the mass fraction of 2.5% of the pseudo-boehmite mass into 1mol/L nitric acid aqueous solution, dropwise adding, and continuously stirring until the materials are uniformly mixed; a wet mass is obtained.
(2) Extruding the wet material mass on an F-26 double-screw extruder (manufactured by general science and technology industries of southern China university) by using a phi 3mm circular orifice plate to form strips, obtaining solid cylindrical strips, cutting the solid cylindrical strips into particles with the length of 3-4 mm, placing the particles in an oven, drying the particles for 24 hours at 40 ℃, then placing the particles in a tube furnace, introducing nitrogen, heating the particles to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 4 hours, stopping heating, cooling the particles to room temperature under the nitrogen atmosphere to obtain a cylindrical strip catalyst, and measuring the crushing strength, specific surface and pore volume of the cylindrical strip catalyst, wherein the results are shown in table 1. XRF elemental analysis showed that the shaped catalyst contained 20.18 wt% carbon, 61.05 wt% nickel and 18.77 wt% alumina. The specific surface, pore volume, pore diameter and crush strength of the catalyst are shown in Table 1.
Application example 1
Crushing the cylindrical catalyst, sieving 0.5 g of 20-40 mesh catalyst particles of example 1 in a continuous flow fixed bed reactor with a reaction gas composition of 38.0% N 2 O, using nitrogen as balance gas, and the flow rate of reaction gas is 15 ml/min. The activity evaluation temperature range is 300-500 ℃, and N is catalytically decomposed 2 The conversion of O is shown in Table 2.
Application example 2
Crushing the cylindrical catalyst, sieving 0.5 g of 20-40 mesh catalyst particles of example 2 in a continuous flow fixed bed reactor with a reaction gas composition of 38.0% N 2 O, using nitrogen as balance gas, and the flow rate of reaction gas is 15 ml/min. The activity evaluation temperature range is 300-500 ℃, and N is catalytically decomposed 2 The conversion of O is shown in Table 2.
Application example 3
Crushing the cylindrical catalyst, sieving 0.5 g of 20-40 mesh catalyst particles of example 3 in a continuous flow fixed bed reactor with a reaction gas composition of 38.0% N 2 O, using nitrogen as balance gas, and the flow rate of reaction gas is 15 ml/min. The activity evaluation temperature range is 300-500 ℃, and 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, using nitrogen as balance gas, and the flow rate of reaction gas is 15 ml/min. The activity evaluation temperature range is 300-500 ℃, and 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 as catalyst was placed in a continuous flow fixed bed reactor with a reaction gas composition of 38.0% N 2 O, using nitrogen as balance gas, and the flow rate of reaction gas is 15 ml/min. The activity evaluation temperature range is 300-500 ℃, and N is catalytically decomposed 2 The conversion of O is shown in Table 2.
Comparative application example 3
Crushing the cylindrical catalyst, sieving 0.5 g of the catalyst particles of comparative example 3 of 20-40 mesh size in a continuous flow fixed bed reactor with a reaction gas composition of 38.0% N 2 O, using nitrogen as balance gas, and the flow rate of reaction gas is 15 ml/min. The activity evaluation temperature range is 300-500 ℃, and N is catalytically decomposed 2 The conversion of O is shown in Table 2.
TABLE 1
TABLE 2
As can be seen from the above tables 1 and 2, the formed catalyst prepared by the method of the present invention not only has higher mechanical strength, but also the doping of alkali metal and/or alkaline earth metal further improves N 2 The O catalytic decomposition performance can meet the requirement of industrial application, and the N can be efficiently eliminated at the temperature of 360-420 DEG C 2 And O. When the formed catalyst provided by the invention is applied to the treatment of the waste gas 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 catalyst of the invention can be maintained or slightly increased.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (12)
1. A method for catalyzing nitrous oxide decomposition is characterized by comprising the steps of contacting a catalyst with nitrous oxide to carry out catalytic decomposition reaction to generate nitrogen and oxygen, wherein the catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier,
the active component is a carbon-coated nickel nanocomposite material, the nanocomposite material 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, 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.
2. The method of claim 1, wherein the nickel content is 16% to 76%, the support content is 10% to 60%, and the carbon content is 6% to 54%, based on the weight of the catalyst.
3. The method of claim 1, wherein the catalyst is prepared by:
providing a carbon-coated nickel nano composite material as raw powder, preparing a second metal salt solution, uniformly mixing the carbon-coated nickel nano composite material and 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 mass;
forming the wet dough, drying the formed body, and performing second roasting treatment in an inert atmosphere to obtain a carbon-coated nickel catalyst;
wherein the second metal salt solution is selected from an alkali metal salt solution and/or an alkaline earth metal salt solution.
4. The method of claim 3, wherein the first firing treatment comprises: heating the dried solid-liquid mixture to 200-500 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature constant for 0.5-10 h; the second roasting treatment comprises: heating the formed product to 400-800 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature constant for 1-10 h.
5. The method of claim 3, wherein the binder is an aluminum sol, a silica sol, or a silica-alumina sol.
6. The method of claim 3, wherein the binder is prepared from pseudoboehmite 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. The method according to claim 3, wherein the liquid-solid mass ratio in the wet mass is 0.8-1.5: 1, the raw powder accounts for 20-80% of the mass of solids in the wet dough.
9. The method according to claim 3, wherein the drying temperature is 20 ℃ to 100 ℃, the drying time is 3h to 24h, and the drying atmosphere is an inert atmosphere or an air atmosphere.
10. A method according to claim 3, wherein the shaping process is selected from one or more of bar extrusion, roller ball and pelletising.
11. The method of claim 3, wherein the carbon-coated nickel nanocomposite comprises a core-shell structure having a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer, the inner core is a nickel nanoparticle, and the carbon content is 15 wt% to 60 wt% and the nickel content is 40 wt% to 85 wt% based on the weight of the carbon-coated nickel nanocomposite.
12. The method according to any one of claims 1 to 11, wherein in the catalytic decomposition reaction, the reaction temperature is 300 ℃ to 420 ℃, the reaction space velocity is 500 ml to 3000 ml of reaction gas/(hr-g catalyst), and the volume concentration of the nitrous oxide is 30% to 40%.
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 true CN115121110A (en) | 2022-09-30 |
| CN115121110B 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117117516A (en) * | 2023-06-02 | 2023-11-24 | 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 (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0075314A2 (en) * | 1981-09-21 | 1983-03-30 | Mta Müszaki Kemiai Kutato Intezet | Bifunctional catalysts that contain gamma-alumina and nickel(II) oxide, and processes for their preparation and their use |
| 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 |
| US20020039550A1 (en) * | 2000-04-22 | 2002-04-04 | Adolf Schafer-Sindlinger | Process and catalyst for reducing nitrogen oxides |
| CN1344178A (en) * | 1999-03-05 | 2002-04-10 | 纳幕尔杜邦公司 | Process for decomposition of nitrous oxide |
| US20020051742A1 (en) * | 2000-09-08 | 2002-05-02 | Masatoshi Hotta | Catalyst for decomposing nitrous oxide, process for producing the same and method for decomposing 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 |
| CN107398283A (en) * | 2017-06-23 | 2017-11-28 | 清华大学 | Catalyst metals heating surface of NOx content and preparation method thereof in a kind of reduction flue gas |
| CN107670669A (en) * | 2017-11-06 | 2018-02-09 | 方文成 | A kind of nitrous oxide decomposes catalysis material and preparation method thereof |
| 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 |
| 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 |
| CN108479218A (en) * | 2018-04-19 | 2018-09-04 | 南京信息工程大学 | A kind of filter bag cage and preparation method thereof with denitration function |
| CN108856706A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of carbon-coating nickel aluminium composite material and its preparation method and application |
| CN109304475A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | Carbon-coating nickel composite material and preparation method |
| 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 (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0075314A2 (en) * | 1981-09-21 | 1983-03-30 | Mta Müszaki Kemiai Kutato Intezet | Bifunctional catalysts that contain gamma-alumina and nickel(II) oxide, and processes for their preparation and their use |
| 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 |
| CN1344178A (en) * | 1999-03-05 | 2002-04-10 | 纳幕尔杜邦公司 | Process for decomposition of nitrous oxide |
| US20020039550A1 (en) * | 2000-04-22 | 2002-04-04 | Adolf Schafer-Sindlinger | Process and catalyst for reducing nitrogen oxides |
| US20020051742A1 (en) * | 2000-09-08 | 2002-05-02 | Masatoshi Hotta | Catalyst for decomposing nitrous oxide, process for producing the same and method for decomposing 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 |
| CN108856706A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of carbon-coating nickel aluminium composite material and its preparation method and application |
| CN107398283A (en) * | 2017-06-23 | 2017-11-28 | 清华大学 | Catalyst metals heating surface of NOx content and preparation method thereof in a kind of reduction flue gas |
| CN109304475A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | Carbon-coating nickel composite material and preparation method |
| 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 |
| 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 |
| CN108479218A (en) * | 2018-04-19 | 2018-09-04 | 南京信息工程大学 | A kind of filter bag cage and preparation method thereof with denitration function |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117117516A (en) * | 2023-06-02 | 2023-11-24 | 太仓碧奇新材料研发有限公司 | Preparation method of organic/inorganic hybrid sub-terahertz wave-absorbing film |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115121110B (en) | 2023-08-08 |
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 | |
| Zhang et al. | Promotional effect for SCR of NO with CO over MnOx-doped Fe3O4 nanoparticles derived from metal-organic frameworks | |
| CN113751004B (en) | Catalyst of carbon-coated transition metal oxide, preparation method and application thereof | |
| Efimov et al. | Comparison of bimetallic Co-Ru nanoparticles supported on highly porous activated carbonized polyacrylonitrile with monometallic ones in ethanol steam reforming | |
| CN115121110B (en) | Method for catalyzing decomposition of nitrous oxide | |
| Ren et al. | Modulated synthesis of MnO2-decorated Fe–Mn composite oxides: synergistic effects on boosting the performance of toluene oxidation | |
| CN112755993B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| Fu et al. | Oxidative decomposition of chlorobenzene on MnaVOX catalysts: The critical roles of oxygen vacancies and hollow structure | |
| CN113750991B (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 | |
| CN113751007B (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 | |
| CN113750781B (en) | Method for catalytic decomposition of nitrous oxide | |
| CN113757696B (en) | Method for catalytic combustion of volatile organic compounds | |
| CN113617357A (en) | Preparation method and application of nickel oxide catalyst for removing VOCs (volatile organic compounds) by coupling low-temperature plasma | |
| 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 | |
| CN112755994A (en) | Carbon-coated nickel-aluminum nano composite material and preparation method and application thereof | |
| CN112755780B (en) | Method for catalytic decomposition of nitrous oxide | |
| CN113751003B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN116078376B (en) | Supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active site, and preparation method and application thereof | |
| CN112755995A (en) | Carbon-coated nickel-aluminum nanocomposite and preparation method and application thereof | |
| CN112762468A (en) | Method for catalytic combustion of volatile organic compounds |
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 |