CN117920340A - Monolithic catalyst, preparation method and application thereof, and method for catalytic combustion of cyclohexane-containing organic waste gas - Google Patents
Monolithic catalyst, preparation method and application thereof, and method for catalytic combustion of cyclohexane-containing organic waste gas Download PDFInfo
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- CN117920340A CN117920340A CN202211303871.1A CN202211303871A CN117920340A CN 117920340 A CN117920340 A CN 117920340A CN 202211303871 A CN202211303871 A CN 202211303871A CN 117920340 A CN117920340 A CN 117920340A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- 239000007789 gas Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 56
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000010815 organic waste Substances 0.000 title claims abstract description 48
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 80
- 239000002808 molecular sieve Substances 0.000 claims abstract description 80
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000011248 coating agent Substances 0.000 claims abstract description 79
- 239000000919 ceramic Substances 0.000 claims abstract description 60
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims abstract description 7
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- 239000000243 solution Substances 0.000 claims description 56
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- 239000002243 precursor Substances 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 28
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 25
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 10
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- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004698 Polyethylene Substances 0.000 claims description 2
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- 239000003570 air Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
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- 239000010948 rhodium Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 239000012855 volatile organic compound Substances 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 3
- XIOPWXFTXDPBEY-UHFFFAOYSA-N ytterbium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XIOPWXFTXDPBEY-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 14
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 13
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a monolithic catalyst for catalytic combustion of cyclohexane-containing organic waste gas, a preparation method and application thereof, and a method for catalytic combustion of cyclohexane-containing organic waste gas. The catalyst comprises a carrier and an active component; wherein the carrier comprises honeycomb ceramics containing TS-1 molecular sieve coating; the active component comprises noble metal and ytterbium oxide. The catalyst can be used for catalytic combustion of cyclohexane-containing organic waste gas, and catalytic combustion of volatile organic compounds such as cyclohexane and the like to generate carbon dioxide and water, and has higher stability and catalyst activity.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an integral catalyst for catalytic combustion of cyclohexane-containing organic waste gas, a preparation method and application thereof, and a method for catalytic combustion of cyclohexane-containing organic waste gas.
Background
The environmental pollution problem is the most troublesome problem facing the world, is closely related to the production and life of human beings, and more serious atmospheric pollution is more and more concerned. Volatile Organic Compounds (VOCs) are a significant source of atmospheric pollution. The most radical and effective method for treating the pollution of the volatile organic compounds is to replace the prior process by adopting a green pollution-free process, and the emission of waste gas is controlled without or with less harmful raw materials. However, due to the limitation of the scientific and technical level, many industries related to civilian life cannot find environment-friendly technology to replace the technology, and various organic waste gases are inevitably discharged to the environment in the production and use processes, such as the use of chemical products of paint, lubricating oil, organic solvents and the like, the synthesis of bulk chemicals, the incineration of industrial waste residues, petrochemical industry and petroleum refining, the production of rubber, the frequent use of pesticides and the like, and a large amount of VOCs are discharged. Most volatile organic compounds have peculiar smell, cause lesions and even cancerogenicity to human bodies, and are discharged into the air to greatly destroy the health of human bodies and the global environment. Therefore, effective treatment of organic waste gas generated in the petrochemical industry process is an important topic in environmental science.
In addition to advocating and developing methods and processes with green, atomic economics, the use of post-treatment to eliminate the pollution that has occurred remains the most viable and practical solution at present. Common post-treatment methods can be classified into two main categories, namely non-destructive techniques, namely recovery methods; another class is known as destructive techniques, i.e., chemical methods. The former includes the common methods of activated carbon adsorption, solution absorption, condensation, membrane separation, etc., which generally achieve enrichment and separation by changing physical conditions in a certain process such as pressure, temperature, etc. The latter mainly comprises biodegradation, catalytic combustion, direct combustion, plasma oxidation, photocatalytic oxidation and other methods, and the methods mainly convert Volatile Organic Compounds (VOCs) into non-toxic or low-toxic inorganic substances such as carbon dioxide, water and the like through chemical or biological technologies. The physical method has the advantages that the volatile organic compounds can be recycled, but the treatment is not thorough, and secondary pollution is easy to cause; the chemical method is characterized by thorough treatment, and the methods which are widely applied mainly comprise a direct thermal combustion method and a catalytic combustion method. The thermal combustion method is to crack harmful substances in the tail gas at high temperature, the temperature of thermal cracking is up to 800-900 ℃, and the method needs to consume a large amount of fuel oil, and has high operation cost, high energy consumption and high treatment cost. The catalytic combustion method reduces the operation temperature to 280-450 ℃ by means of the action of the catalyst, greatly reduces the energy consumption, is safe and stable to operate, reduces the operation cost, does not produce nitrogen oxides, and therefore does not produce secondary pollution. Therefore, catalytic combustion is an ideal method for treating petrochemical organic waste gas.
The catalyst for catalytic combustion mainly comprises a noble metal catalyst and a non-noble metal catalyst, and compared with the non-noble metal catalyst, the noble metal catalyst has the characteristics of high activity and good stability. However, noble metals are rare and expensive, so that noble metals are generally supported on a certain carrier when preparing noble metal catalysts. The more commonly used supports are typically alumina supports or transition metal supports. It is common practice to prepare catalytic combustion catalysts by coating an alumina or transition metal oxide onto a honeycomb support and then loading the precious metal onto the alumina or transition metal oxide coated honeycomb support.
CN102441379a and CN1415410a belong to the class of noble metals supported on the above-mentioned alumina or transition metal oxide coated honeycomb supports. The lower specific surface area of alumina and transition metal oxides results in lower catalyst activity.
Disclosure of Invention
The invention aims to solve the problems of low activity, poor stability and the like of an integral catalyst in the prior art, and provides the integral catalyst for catalyzing and burning cyclohexane-containing organic waste gas, which has the advantage of better stability.
In order to achieve the above object, a first aspect of the present invention provides a monolith catalyst for catalytic combustion of cyclohexane-containing organic exhaust gas, the catalyst comprising a support and an active component; wherein the carrier comprises honeycomb ceramics containing TS-1 molecular sieve coating; the active component comprises noble metal and ytterbium oxide.
The second aspect of the present invention provides a method for preparing the above monolithic catalyst, comprising:
(1) Coating a raw material for providing a TS-1 molecular sieve coating on honeycomb ceramics, and then carrying out first drying and first roasting to obtain a carrier;
(2) The carrier is contacted with precursor solution containing noble metal and ytterbium, and then separated, dried, calcined and reduced.
In a third aspect, the invention provides the use of the catalyst described above in the catalytic combustion of cyclohexane-containing organic waste gases.
In a fourth aspect, the invention provides a method for catalytic combustion of cyclohexane-containing organic waste gas, the method comprising: introducing oxygen-containing gas, and contacting the catalyst with cyclohexane-containing organic waste gas at 200-450 ℃.
The catalyst can be used for treating cyclohexane-containing organic waste gas, volatile organic matters such as cyclohexane and the like are catalytically combusted to generate carbon dioxide and water, the catalyst activity is high, the cyclohexane conversion rate is more than 99 percent and the selectivity of the final product carbon dioxide is more than 99 percent when the temperature of a catalyst bed is not higher than 350 ℃ under the condition that the concentration of the cyclohexane-containing organic waste gas is 8000mg/m 3, and the catalyst can be widely applied to catalytic combustion reactions of industrial organic waste gas such as cyclohexane-containing petrochemical organic waste gas and the like.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. 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 are to be considered as specifically disclosed herein.
The first aspect of the invention provides a monolithic catalyst for catalytic combustion of cyclohexane-containing organic waste gas, the catalyst comprising a support and an active component; wherein the carrier comprises honeycomb ceramics containing TS-1 molecular sieve coating; the active component comprises noble metal and ytterbium oxide.
In the invention, the honeycomb ceramics has better thermal stability and dispersity as an integer carrier, but the surface area is lower, as the alumina or the transition metal oxide is often coated on the honeycomb ceramics in the prior art, the specific surface areas of the alumina and the transition metal oxide are lower, so that the catalyst activity is lower, the expansion coefficient difference of the alumina and the transition metal oxide is larger, and when the organic waste gas is burnt, the coating is dropped due to the continuous change of the temperature, so that the service life of the catalyst is shortened, namely the stability of the catalyst is poor. In the present invention, the inventors used a specific honeycomb ceramic coated with a TS-1 molecular sieve coating as a carrier, and then the interaction between the noble metal and ytterbium supported on the carrier and the specific carrier could not only increase the activity of the catalyst, but also increase the stability of the catalyst.
According to the invention, in some preferred embodiments, the TS-1 molecular sieve coating is present in an amount of 3 to 25wt% (e.g., 3wt%, 4wt%, 6wt%, 8wt%, 10wt%, 14wt%, 15wt%, 20wt%, 23wt%, or 25 wt%), preferably 6 to 14wt%, based on the mass of the honeycomb ceramic. With the foregoing embodiment, the activity of the entire catalyst can be further increased.
According to the present invention, the honeycomb ceramic may be any type of honeycomb ceramic including, but not limited to, cordierite honeycomb ceramic, aluminum titanate honeycomb ceramic and mullite honeycomb ceramic, the advantages of the present invention being exemplified by cordierite honeycomb ceramic, but the present invention is not limited thereto.
In the present invention, it is understood that the TS-1 molecular sieve is a titanium silicalite molecular sieve, and the TS-1 molecular sieve coating contains titanium element, i.e., the catalyst also contains titanium element, and in some embodiments, the titanium content of the catalyst is 0.1 to 5g/L, preferably 0.3 to 2.6g/L (e.g., 0.3g/L, 0.75g/L, 1g/L, 1.2g/L, 1.5g/L, 1.8g/L, 2.3g/L, 2.6g/L, 4g/L, or 5 g/L), and more preferably 1to 2.6g/L, based on the volume of the support and the titanium element. Under the previous embodiment, the overall activity and stability of the catalyst can be further increased, the inventor speculates that the TS-1 molecular sieve coating can better adsorb noble metals and ytterbium, meanwhile, the interaction of the TS-1 molecular sieve coating and the noble metals and ytterbium can increase the activation capability of bonds such as O 2, C-H, O-H and the like, and in addition, the interaction of the TS-1 molecular sieve coating structure and the noble metals and ytterbium can prevent active components such as the noble metals and ytterbium and the like from being exposed to toxic substances, so that the stability of the catalyst is further enhanced.
In accordance with the present invention, it is also understood that in some embodiments, the feedstock providing a TS-1 molecular sieve coating comprises a coating solution comprising TS-1 molecular sieve. Namely, the honeycomb ceramics containing the TS-1 molecular sieve coating is formed by coating the honeycomb ceramics with coating liquid containing the TS-1 molecular sieve.
According to the present invention, the composition of the coating liquid containing the TS-1 molecular sieve is not particularly limited as long as the object of the present invention can be achieved, and in some embodiments, the coating liquid includes the TS-1 molecular sieve, a pore-forming agent, a viscosity regulator and water, and with the foregoing embodiments, a TS-1 molecular sieve coating having excellent coating properties can be obtained, and the activity and stability of the catalyst can be increased.
According to the present invention, in some embodiments, the mass ratio of TS-1 molecular sieve to water is (0.05-0.8): 1.
According to the present invention, in some embodiments, the mass ratio of TS-1 molecular sieve to pore former is 1: (0.1-0.5).
According to the present invention, in some embodiments, the mass ratio of TS-1 molecular sieve to viscosity modifier is 1: (0.02-0.18).
According to the present invention, in some embodiments, the pore-forming agent is selected from one or more of polyvinyl alcohol, carboxymethyl cellulose, cetyltrimethylammonium bromide, polyethylene glycol, P123 polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and poloxamer. Under the action of the pore-forming agent, a catalyst with high activity and stability can be obtained.
In accordance with the present invention, in order to form the TS-1 molecular sieve coating, in some embodiments, the viscosity modifier is selected from one or more of nitric acid, acetic acid, boric acid, oxalic acid, and phosphoric acid, preferably nitric acid. With the foregoing embodiments, the activity and stability of the catalyst are higher.
According to the present invention, the noble metal has catalytic oxidation activity, and the specific kind of the noble metal is not particularly limited as long as the object of the present invention can be achieved, and in some embodiments, the noble metal is selected from one or more of platinum, rhodium, palladium, gold and silver, preferably platinum and palladium. With the foregoing embodiments, the activity and stability of the catalyst can be further increased.
According to the present invention, the specific contents of platinum and palladium in the catalyst are not limited as long as the object of the present invention is achieved, and in some embodiments, the molar ratio of platinum and palladium in the catalyst is (0.015-2) in terms of platinum element and palladium element: 1, preferably (0.1-0.5): 1. the catalyst which is used for the synergistic interaction between platinum, palladium and molecular sieve coatings and carriers in the system can be increased by adopting the embodiment, and the activation of C-H and C-O bonds in cyclohexane-containing organic waste gas is further increased, so that the activity of the catalyst is further increased.
According to the present invention, the palladium content of the catalyst is, in some embodiments, greater than 100mg/L, preferably 120-1600mg/L, more preferably 120-400mg/L, based on the volume of the support and the palladium element. With the foregoing embodiments, the activity and stability of the catalyst can be increased.
According to the invention, the ytterbium content of the catalyst is in some embodiments 0.2 to 2g/L, preferably 0.3 to 1.8g/L, based on the volume of the support and on the ytterbium element. With the foregoing embodiments, the activity and stability of the catalyst can be increased.
The second aspect of the present invention provides a method for preparing the above catalyst, comprising:
(1) Coating a raw material for providing a TS-1 molecular sieve coating on honeycomb ceramics, and then carrying out first drying and first roasting to obtain a carrier;
(2) The carrier is contacted with precursor solution containing noble metal and ytterbium, and then separated, dried, calcined and reduced.
In the present invention, it is understood that the conditions of the reduction can be controlled by those skilled in the art such that the noble metal is reduced, resulting in the monolithic catalyst of the present invention comprising an active component comprising a noble metal and ytterbium oxide.
According to the present invention, the contact of the support with the platinum-palladium-ytterbium-containing precursor solution may be carried out under a static (e.g., static impregnation) or dynamic condition (e.g., stirring) as required, so long as the object of the present invention can be achieved, and the present invention is not particularly limited thereto.
In the invention, the catalyst prepared by the method has high activity and stability.
According to the invention, the materials for providing the TS-1 molecular sieve coating can be mixed into coating liquid according to the need, and the coating liquid is coated on honeycomb ceramics, and in some embodiments, the coating liquid containing the TS-1 molecular sieve is obtained after the materials for providing the TS-1 molecular sieve coating are stirred, mixed and colloid-milled; the mixing and colloid milling modes can be carried out according to the needs, and are not particularly limited, for example, stirring and mixing for 0.5-4h and colloid milling for 0.5-3h.
In the present invention, the coating, the first drying, and the first calcination may be performed a plurality of times according to the amount of the TS-1 molecular sieve coating. And may be applied according to a manner selected from the group consisting of spraying, dipping, brushing, and the like.
In the present invention, high pressure nitrogen gas can be used to blow out the residual liquid in the honeycomb ceramics after each coating, which is a conventional operation in the art, and the description thereof is not repeated.
In order to better bond the TS-1 molecular sieve coating to the honeycomb ceramic according to the present invention, the conditions of the first drying and the first firing in the preparation method are not limited as long as the object of the present invention can be achieved, and in some embodiments, the conditions of the first drying include: the first drying temperature is 100-120 ℃, and the first drying time is 1-15h.
According to the present invention, in some embodiments, the conditions of the first firing include: the first roasting temperature is 350-600 ℃, and the first roasting time is 3-8h.
According to the present invention, the first drying and the first firing may be performed by selecting a stage-wise heating manner as needed, and in some embodiments, the first drying is performed by heating from 20 to 30 ℃ to 100 to 120 ℃ for 1 to 15 hours at a heating rate of 0.5 to 1.5 ℃/min, and then the first firing is performed by heating from 100 to 120 ℃ to 350 to 600 ℃ for 3 to 8 hours at 0.5 to 1.5 ℃/min.
In the invention, the catalyst carrier with excellent performance can be obtained by adopting the conditions of the first drying and the first roasting, thereby increasing the activity and the stability of the catalyst.
In order to further increase the interaction of the individual components in the catalyst according to the present invention, in some embodiments, the conditions of the second drying include: the second drying temperature is 90-120 ℃, and the second drying time is 1-10h; in some embodiments, the conditions of the second firing include: the second roasting temperature is 500-600 ℃, and the second roasting time is 4-8h.
According to the present invention, the reduction may be carried out by a reduction method conventional in the art, the specific conditions of which are not particularly limited, and in some embodiments, the conditions of the reduction include: reducing by using hydrogen with the volume concentration of 5-25%, wherein the reduction temperature is 300-400 ℃. With the foregoing embodiments, the performance of the catalyst can be further improved. The noble metal can be reduced under the aforementioned reducing conditions to obtain the monolithic catalyst containing the active components including noble metal and ytterbium oxide of the present invention. In the present invention, the active site in the active component is on the ytterbium atom in the noble metal and ytterbium oxide.
In the present invention, the other gas in the reduction of hydrogen gas having a volume concentration of 5 to 25% is not particularly limited as long as it has no influence on the reduction reaction, for example, nitrogen gas.
According to the present invention, it is understood that the precursor solution containing the noble metal and ytterbium refers to a solution of the precursor of the noble metal and the precursor of ytterbium and other optional components in a solvent, wherein the kind of solvent may be selected according to need, including but not limited to water.
According to the present invention, the concentration of the precursor solution containing the noble metal and ytterbium, in which the concentration of the precursor of the noble metal is 0.20 to 1.5g/L in terms of noble metal element in some embodiments, is not particularly limited as long as the object of the present invention can be achieved.
According to the present invention, in some embodiments, the concentration of ytterbium precursor in the precursor solution is 0.005-0.05mol/L. With the foregoing embodiments, the performance of the catalyst can be further improved
According to the present invention, in some preferred embodiments, the noble metal comprises platinum and palladium.
According to the present invention, the platinum precursor, the palladium precursor, and the ytterbium precursor are raw materials providing platinum, palladium, and ytterbium, respectively, and in some embodiments, the platinum precursor, the palladium precursor, and the ytterbium precursor are each a soluble acid or a soluble salt.
According to the present invention, in some preferred embodiments, the platinum precursor and the palladium precursor are each selected from one or more of nitrate, acetate, oxalate, and soluble acid.
In accordance with the present invention, in some preferred embodiments, the ytterbium precursor is selected from one or more of nitrate, acetate, and oxalate.
According to the present invention, the TS-1 molecular sieve may be a molecular sieve commonly used in the art, and may be obtained commercially, or may be obtained by self-preparation, and the source thereof is not particularly limited, and in some embodiments, the TS-1 molecular sieve may be prepared by a process comprising: tetraethyl silicate is sequentially contacted with tetrapropylammonium hydroxide aqueous solution, tetrabutyl titanate-containing solution and phosphoric acid, and then crystallized and roasted.
According to the present invention, the contact of tetraethyl silicate with each of the aqueous tetrapropylammonium hydroxide solution, tetrabutyl titanate-containing solution and phosphoric acid may be carried out, for example, under static or dynamic (e.g., stirring) conditions, as desired.
The concentration of the aqueous tetrapropylammonium hydroxide solution may be selected as desired in accordance with the invention, and in some embodiments, the concentration of the aqueous tetrapropylammonium hydroxide solution is 10-25wt%.
According to the present invention, the solvent in the tetrabutyl titanate-containing solution may be selected as desired without particular limitation, including but not limited to isopropanol, and in some embodiments the tetrabutyl titanate-containing solution has a concentration of from 10 to 15 weight percent.
In accordance with the present invention, in some preferred embodiments, a method for preparing a TS-1 molecular sieve comprises: and (3) dropwise adding a tetrapropylammonium hydroxide aqueous solution into tetraethyl silicate, adding a tetrabutyl titanate solution dissolved in isopropanol under stirring, stirring for 0.2-1h after the tetrabutyl titanate solution is added, dropwise adding phosphoric acid, continuously stirring for 0.5-2h after the dropwise adding is finished, and crystallizing and roasting.
According to the invention, in the preparation method of the TS-1 molecular sieve, dripping is a method commonly used in the field, and a person skilled in the art can select according to the need, so that excessive description is not needed in the invention.
According to the present invention, in some embodiments, the molar ratio of tetrapropylammonium hydroxide to tetraethyl silicate is (0.3-0.8): 1.
According to the present invention, in some embodiments, the molar ratio of tetrabutyl titanate to tetraethyl silicate is (0.005-0.05): 1.
According to the invention, in some embodiments, the molar ratio of phosphoric acid to tetraethyl silicate is (0.02-0.08): 1.
According to the present invention, conditions for crystallization and firing may be selected as desired, and in some embodiments, the conditions for crystallization include: the crystallization temperature is 130-180 ℃ and the crystallization time is 4-10h.
According to the present invention, in some embodiments, the conditions of firing include: the roasting temperature is 400-550 ℃ and the roasting time is 4-12h.
In the invention, the TS-1 molecular sieve prepared by the method is used for preparing honeycomb ceramics containing a TS-1 molecular sieve coating, and meanwhile, the catalyst has higher activity and stability through interaction synergistic effect with noble metals and ytterbium.
In a third aspect, the invention provides the use of the catalyst described above in the catalytic combustion of cyclohexane-containing organic waste gases.
In the invention, the catalyst has higher activity and stability when catalyzing and burning cyclohexane-containing organic waste gas.
In a fourth aspect, the invention provides a method for catalytic combustion of cyclohexane-containing organic waste gas, the method comprising: introducing oxygen-containing gas, and contacting the catalyst with cyclohexane-containing organic waste gas at 200-450 ℃.
According to the invention, the cyclohexane content in the cyclohexane-containing organic waste gas is 500-15000mg/m 3.
According to the present invention, oxygen-containing gases capable of promoting combustion are suitable for use in the present system, and the present invention is not particularly limited in this regard, and in some embodiments the oxygen-containing gases include a mixture of nitrogen and oxygen or air.
In the invention, the catalyst can catalyze and burn organic waste gas containing cyclohexane better, and when the conversion rate of cyclohexane reaches more than 99%, the required temperature is lower, which proves that the catalyst has excellent activity.
The present invention will be described in detail by examples. In the following examples and comparative examples:
The evaluation method of the catalyst comprises the following steps: at a gas space velocity of 15000h -1, the cyclohexane-containing organic waste gas is subjected to catalytic combustion reaction under the condition of an oxygen content of 10% by volume. The cyclohexane content in the cyclohexane-containing organic waste gas is 8000mg/m 3;
Example 1
Synthesis of TS-1 molecular sieve: aqueous tetrapropylammonium hydroxide solution (concentration 20 wt%) was slowly added dropwise to tetraethyl silicate (molar ratio of tetrapropylammonium hydroxide to tetraethyl silicate 0.55); then, a solution of tetrabutyl titanate (concentration: 12.5 wt%) dissolved in isopropyl alcohol was added to the above solution with stirring (molar ratio of tetrabutyl titanate to tetraethyl silicate: 0.03); stirring for 0.5h after the addition, dripping phosphoric acid into the solution (the mol ratio of phosphoric acid to tetraethyl silicate is 0.055:1), continuously stirring for 1h after the dripping, crystallizing for 6h at 160 ℃, and roasting for 6h at 450 ℃ to obtain the TS-1 molecular sieve;
TS-1 molecular sieve coating: mixing a TS-1 molecular sieve, carboxymethyl cellulose, nitric acid and water according to a mass ratio (the mass ratio of the TS-1 molecular sieve to the carboxymethyl cellulose is 3.3, the mass ratio of the TS-1 molecular sieve to the nitric acid is 13.5, and the mass ratio of the TS-1 molecular sieve to the water is 0.28), stirring for 30 minutes, and then colloid milling for 30 minutes to obtain a coating liquid; soaking honeycomb ceramics (cordierite honeycomb ceramics) in the slurry for 30 minutes, taking out, blowing out residual night in the honeycomb ceramics by using high-pressure nitrogen, standing for 1 hour at room temperature, keeping the temperature from 20 ℃ to 110 ℃ for 3 hours at the heating rate of 1 ℃/min, drying, keeping the temperature from 110 ℃ to 550 ℃ for 5 hours at the heating rate of 1 ℃/min, roasting to obtain honeycomb ceramics containing TS-1 molecular sieve coating, and repeating the steps of soaking, drying and roasting until the honeycomb ceramics containing TS-1 molecular sieve coating with the content of 4wt% is obtained;
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain precursor solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.35mg/mL, the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then dried at 110 ℃ for 5h, baked at 550 ℃ for 6h, and finally reduced at 350 ℃ for 3 h in 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 2
The procedure of example 1 was followed, except that:
Repeating the steps of coating, drying and roasting until the honeycomb ceramics containing the TS-1 molecular sieve coating, the content of which is 8 weight percent, is obtained;
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.35mg/mL, the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then the honeycomb ceramics is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 3
The procedure of example 1 was followed, except that:
Repeating the steps of coating, drying and roasting until the honeycomb ceramics containing the TS-1 molecular sieve coating, the content of which is 14 weight percent, is obtained;
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.35mg/mL, the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then the honeycomb ceramics is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 4
The procedure of example 2 was followed, except that:
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.008mol/L, the Pt content is 0.35mg/mL, the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 5
The procedure of example 2 was followed, except that:
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.047mol/L, the Pt content is 0.35mg/mL and the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on a honeycomb containing a TS-1 molecular sieve coating, then the honeycomb is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 6
The procedure of example 2 was followed, except that:
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.14mg/mL, the Pd content is 0.31 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then the honeycomb ceramics is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 7
The procedure of example 2 was followed, except that:
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.57mg/mL, the Pd content is 1.23 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then the honeycomb ceramics is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 8
The procedure of example 2 was followed, except that:
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.17mg/mL, the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 9
The procedure of example 2 was followed, except that:
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.54mg/mL, the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then the honeycomb ceramics is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 10
The procedure of example 2 was followed, except that:
polyvinyl alcohol (polyvinyl alcohol 124) was used instead of carboxymethyl cellulose.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 11
The procedure of example 2 was followed, except that:
Polyethylene glycol (polyethylene glycol 300) was used instead of carboxymethyl cellulose.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 12
The procedure of example 2 was followed, except that:
Repeating the steps of coating, drying and roasting until the honeycomb ceramic containing the TS-1 molecular sieve coating with the TS-1 molecular sieve coating content of 25 weight percent is obtained.
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.35mg/mL, the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then the honeycomb ceramics is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 13
The procedure of example 2 was followed, except that:
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03mol/L, the Pt content is 0.11mg/mL, the Pd content is 0.25 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics containing TS-1 molecular sieve coating, then the honeycomb ceramics is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally the monolithic catalyst is reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere.
Example 14
The precursor solution in example 2 was mixed with the coating solution in example 2 (the amount of which is 8wt% of the honeycomb ceramic based on the TS-1 molecular sieve) to obtain a mixed solution, and then the mixed solution was coated on the honeycomb ceramic, followed by drying at 110℃for 5 hours, baking at 550℃for 6 hours, and finally reduction at 350℃for 3 hours in a 10% hydrogen atmosphere to obtain a monolithic catalyst.
Example 15
TS-1 molecular sieve coating: mixing TS-1 molecular sieve, nitric acid and water according to the mass ratio (the mass ratio of TS-1 molecular sieve to nitric acid is 13.5, and the mass ratio of TS-1 molecular sieve to water is 0.28), stirring for 30 minutes, and then colloid milling for 30 minutes to obtain coating liquid;
A honeycomb ceramic containing a TS-1 molecular sieve coating having a TS-1 molecular sieve coating content of 8wt% was obtained as in example 2, followed by the preparation of a monolith catalyst as in example 2.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Example 16
The catalyst was evaluated for 500 hours as in example 2. The catalyst has stable performance, and the cyclohexane conversion rate is always kept at 99% under the condition of unchanged reaction conditions.
Comparative example 1
Alumina coating: mixing alumina coating, carboxymethyl cellulose, nitric acid and water according to the mass ratio (the mass ratio of alumina to carboxymethyl cellulose is 3.3, the mass ratio of alumina to nitric acid is 13.5, and the mass ratio of alumina to water is 0.28), stirring for 30 minutes, and then colloid milling for 30 minutes to obtain coating liquid; soaking the honeycomb ceramic in the slurry for 30 minutes, taking out, blowing out residual night in the honeycomb ceramic by using high-pressure nitrogen, standing for 1 hour at room temperature, keeping the temperature from 20 ℃ to 110 ℃ for 3 hours at the heating rate of 1 ℃/min, then keeping the temperature from 110 ℃ to 550 ℃ for 5 hours at the heating rate of 1 ℃/min, roasting to obtain the honeycomb ceramic containing the TS-1 molecular sieve coating, and repeating the steps of coating, drying and roasting until the honeycomb ceramic containing the alumina coating with the alumina coating content of 8 weight percent is obtained;
Preparation of the monolith catalyst: ytterbium nitrate pentahydrate, chloroplatinic acid and palladium chloride are dissolved in water to obtain a solution (the concentration of ytterbium nitrate pentahydrate is 0.03 mol/L), the Pt content is 0.35mg/mL, the Pd content is 0.77 mg/mL), the precursor solution is equivalently immersed on honeycomb ceramics (cordierite honeycomb ceramics) containing an alumina coating, then the honeycomb ceramics is dried at 110 ℃ for 5 hours, baked at 550 ℃ for 6 hours, and finally reduced at 350 ℃ for 3 hours in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
The cyclohexane-containing organic waste gas was subjected to catalytic combustion reaction under the catalyst, and the reaction results are shown in table 1.
Comparative example 2
The procedure of example 2 was followed, except that:
Preparation of the monolith catalyst: dissolving chloroplatinic acid and palladium chloride in water to obtain a solution (Pt content is 0.35mg/mL and Pd content is 0.77 mg/mL), immersing the precursor solution on honeycomb ceramics containing a TS-1 molecular sieve coating in equal quantity, drying at 110 ℃ for 5h, roasting at 550 ℃ for 6h, and finally reducing at 350 ℃ for 3 h in a 10% hydrogen atmosphere to obtain the monolithic catalyst.
TABLE 1
T1 in Table 1 represents: the lowest combustion temperature at 99% cyclohexane conversion, the lower the temperature, the higher the activity of the catalyst; the coating amount in comparative example 1 was 8% in terms of alumina; the examples and comparative examples therefore measure the performance of the catalyst in terms of the minimum combustion temperature (T1) at which the cyclohexane conversion reaches more than 99%.
As can be seen from the results of Table 1, examples 1-15 employing the present invention have lower combustion temperatures, i.e., the catalyst performance is better.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A monolithic catalyst for catalytic combustion of cyclohexane-containing organic waste gas, characterized in that the catalyst comprises a support and an active component;
Wherein the carrier comprises honeycomb ceramics containing TS-1 molecular sieve coating;
the active component comprises noble metal and ytterbium oxide.
2. The catalyst according to claim 1, wherein,
The TS-1 molecular sieve coating is 3 to 25 weight percent, preferably 6 to 14 weight percent, based on the mass of the honeycomb ceramic; and/or
The titanium content of the catalyst is 0.1-5g/L, preferably 0.3-2.6g/L, more preferably 1-2.6g/L, based on the volume of the carrier and titanium element; and/or
The raw materials for providing the TS-1 molecular sieve coating comprise coating liquid containing TS-1 molecular sieve.
3. The catalyst according to claim 2, wherein,
The coating liquid comprises TS-1 molecular sieve, pore-forming agent, viscosity regulator and water;
preferably, the mass ratio of the TS-1 molecular sieve to water is (0.05-0.8): 1, a step of; and/or
The mass ratio of the TS-1 molecular sieve to the pore-forming agent is 1: (0.1-0.5); and/or
The mass ratio of the TS-1 molecular sieve to the viscosity modifier is 1: (0.02-0.18);
Preferably, the pore-forming agent is selected from one or more of polyvinyl alcohol, carboxymethyl cellulose, cetyl trimethyl ammonium bromide, polyethylene glycol, P123 polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and poloxamer; and/or
The viscosity modifier is selected from one or more of nitric acid, acetic acid, boric acid, phosphoric acid and oxalic acid, preferably nitric acid.
4. A catalyst according to any one of claim 1 to 3, wherein,
The noble metal is selected from one or more of platinum, rhodium, palladium, gold and silver, preferably platinum and palladium;
Preferably, the catalyst has a molar ratio of platinum to palladium, calculated as elemental platinum and elemental palladium, of (0.015-2): 1, preferably (0.1-0.5): 1, a step of; and/or
The content of palladium in the catalyst is more than 100mg/L, preferably 120-1600mg/L, and more preferably 120-400mg/L, calculated on the basis of the volume of the carrier and the palladium element;
And/or the number of the groups of groups,
The ytterbium content of the catalyst is 0.2-2g/L, preferably 0.3-1.8g/L, based on the volume of the support and the ytterbium element.
5. A process for the preparation of a monolithic catalyst according to any one of claims 1 to 4, comprising:
(1) Coating a raw material for providing a TS-1 molecular sieve coating on honeycomb ceramics, and then carrying out first drying and first roasting to obtain a carrier;
(2) The carrier is contacted with precursor solution containing noble metal and ytterbium, and then separated, dried, calcined and reduced.
6. The preparation method according to claim 5, wherein,
The conditions of the first drying include: the first drying temperature is 100-120 ℃, and the first drying time is 1-15h; and/or
The conditions for the first firing include: the first roasting temperature is 350-600 ℃, and the first roasting time is 3-8h; and/or
The conditions of the second drying include: the second drying temperature is 90-120 ℃, and the second drying time is 1-10h; and/or
The conditions for the second firing include: the second roasting temperature is 500-600 ℃, and the second roasting time is 4-8h; and/or
The conditions for the reduction include: reducing by using hydrogen with the volume concentration of 5-25%, wherein the reduction temperature is 300-400 ℃.
7. The preparation method according to claim 5 or 6, wherein,
In the precursor solution, the concentration of the precursor of noble metal is 0.20-1.5g/L calculated by noble metal element; and/or
In the precursor solution, the concentration of the ytterbium precursor is 0.005-0.05mol/L;
Preferably, the noble metal includes platinum and palladium;
Further preferably, the platinum precursor, the palladium precursor, and the ytterbium precursor are each a soluble acid or a soluble salt;
Still further preferably the method comprises the steps of,
The platinum precursor and the palladium precursor are each selected from one or more of nitrate, acetate, oxalate and soluble acid; and/or
The ytterbium precursor is selected from one or more of nitrate, acetate and oxalate.
8. The process according to any one of claim 5 to 7, wherein,
The preparation method of the TS-1 molecular sieve comprises the following steps: tetraethyl silicate is sequentially contacted with tetrapropylammonium hydroxide aqueous solution, tetrabutyl titanate-containing solution and phosphoric acid, and then crystallized and roasted;
preferably, the method comprises the steps of,
The molar ratio of tetrapropylammonium hydroxide to tetraethyl silicate is (0.3-0.8): 1, a step of; and/or
The molar ratio of tetrabutyl titanate to tetraethyl silicate is (0.005-0.05): 1, a step of; and/or
The mole ratio of phosphoric acid to tetraethyl silicate is (0.02-0.08): 1, a step of; and/or
The crystallization conditions include: the crystallization temperature is 130-180 ℃ and the crystallization time is 4-10h; and/or
The roasting conditions include: the roasting temperature is 400-550 ℃ and the roasting time is 4-12h.
9. Use of a catalyst according to any one of claims 1 to 4 for the catalytic combustion of cyclohexane-containing organic waste gases.
10. A method for catalytic combustion of cyclohexane-containing organic waste gas, the method comprising: introducing an oxygen-containing gas, and contacting the catalyst of any one of claims 1-4 with cyclohexane-containing organic waste gas at a temperature of 200-450 ℃;
Preferably, the cyclohexane-containing organic waste gas has a cyclohexane content of 500-15000mg/m 3; and/or
The oxygen-containing gas includes a mixture of nitrogen and oxygen or air.
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