CN115845912A - Composite transition metal molecular sieve catalyst, and preparation method and application thereof - Google Patents
Composite transition metal molecular sieve catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 5
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 16
- 239000002243 precursor Substances 0.000 abstract description 10
- 239000002912 waste gas Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
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- 230000032683 aging Effects 0.000 description 8
- 238000007084 catalytic combustion reaction Methods 0.000 description 8
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- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- MKKVKFWHNPAATH-UHFFFAOYSA-N [C].N Chemical class [C].N MKKVKFWHNPAATH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a composite transition metal molecular sieve catalyst, a preparation method and application thereof, wherein the catalyst is prepared from an active component, an auxiliary agent, a carrier and a dispersing agent; the active component precursor is one or the combination of more than two of nitrate, acetate and sulfate of transition metal elements, and the auxiliary agent precursor is one or the combination of more than two of nitrate, acetate and sulfate of rare earth elements; the carrier is one or the combination of more than two of Y-type molecular sieve, ZSM-type molecular sieve and mordenite; the dispersant is one or the combination of more than two of citric acid, polyethylene glycol, ethylene glycol and hexadecyl trimethyl ammonium bromide. The catalyst prepared by the invention has the advantages of simple technical process, low cost, high waste gas treatment and purification efficiency, no secondary pollution and long service life.
Description
Technical Field
The invention belongs to the field of VOCs waste gas catalytic combustion treatment, and particularly relates to a composite transition metal molecular sieve catalyst and a preparation method and application thereof.
Background
The source of volatile organic pollutants (VOCs) is closely related to the social industrial production and widely exists in the production and life of people; the method has the characteristics of multiple generation types, large quantity and strong harmfulness, and brings great harm to the production and the life of human beings. For example, most VOCs are easy to generate the risks of flammability, explosiveness and the like, and in addition, the gas of the VOCs can have serious influence on the environment, such as the fluorochlorohydrocarbons and the carbon ammonia compounds can cause serious damage to the ozone layer; once the ozone is discharged into the atmosphere, the concentration of the ozone in the atmosphere is rapidly reduced, and a room effect is caused. Meanwhile, VOCs are the main culprit of forming photochemical smog, and CH compounds and oxynitride in the atmosphere can also generate photochemical reaction under the action of ultraviolet light to generate secondary pollutants, namely photochemical smog.
The VOCs treatment in the prior industry adopts single activated carbon adsorption or activated carbon adsorption plus photocatalysis treatment, and has the defects of low overall treatment efficiency and poor stability. The catalytic combustion technology has the advantages of simple equipment, low combustion temperature, low energy consumption, difficult formation of NOx secondary pollution, high removal efficiency and the like, and is one of the most effective methods for eliminating the pollution of medium-low concentration VOCs. However, the performance of the catalyst is a key problem for determining a catalytic combustion technology, and the current industrial common VOCs catalysts mainly comprise noble metals (Pd, pt and the like) and transition metal oxides (Cu, mn and the like), and the noble metal catalysts have the advantages of low ignition temperature and high low-temperature catalytic activity, but have high cost and poor poisoning resistance, so that the large-scale application is limited.
Based on the analysis, the raw material is simple and easy to obtain, has low price, and can directly decompose VOCs into CO 2 And H 2 O, no secondary pollution, difficult inactivation and wide application in the field of VOCs waste gas catalytic combustion treatment in typical industries and a preparation method thereofIs urgently needed in the industry at present.
Disclosure of Invention
In view of the defects, the invention provides a composite transition catalyst and a preparation method thereof, which take the research and development of a transition metal molecular sieve catalyst as a core, utilize the large specific surface area and the developed pore structure of a molecular sieve material as a carrier, and adopt the preparation processes of vacuum rapid drying and the like to improve the dispersity and the adhesive strength of active components of the catalyst.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a composite transition metal molecular sieve catalyst comprising:
active components, auxiliary agents, carriers and dispersing agents;
wherein:
the active component is one or more of nitrate, acetate and sulfate of transition metal elements;
the auxiliary agent is one or more of nitrate, acetate and sulfate of rare earth elements;
the carrier is any one or more of Y-type molecular sieve, ZSM-type molecular sieve and mordenite;
the dispersant is one or more of citric acid, polyethylene glycol, ethylene glycol and cetyl trimethyl ammonium bromide.
Further, the active components are any two of nitrate, acetate and sulfate of transition metal elements.
Further, the mass ratio of nitrate, acetate and sulfate of any two transition metal elements in the active components is 1: (0.5-3).
Further, the transition metal element is any one or more of cobalt, copper, nickel, manganese, iron and chromium; the rare earth element is one or the mixture of more than two of lanthanum and cerium.
Further, the total weight of the active component and the auxiliary agent accounts for 5-25% of the carrier.
Further, the mass ratio of the auxiliary agent to the active component is 1: (0.2-1).
The invention also discloses a preparation method of the composite transition metal molecular sieve catalyst, which comprises the following steps:
adding water into the active component and the auxiliary agent to prepare an active component solution;
fully mixing the carrier and the dispersing agent in the active component solution, adjusting the pH value of the solution by using a precipitator, and carrying out coprecipitation;
washing, filtering, vacuum drying and roasting the precipitate to obtain the catalyst.
Further, the coprecipitation time of the carrier is 12-24 h; the drying temperature is 100-150 ℃, and the drying time is 12-24 h; the roasting temperature is 500-600 ℃, and the roasting time is 2-8 h.
Further, the precipitator is any one or more of ammonia water, urea and sodium carbonate.
Further, the pH is adjusted to 7 to 11.
The invention also discloses a composite transition metal molecular sieve catalyst prepared by any one of the preparation methods.
The invention also discloses an application of the compound transition metal molecular sieve catalyst in preparation of low Wen Tuochu VOCs.
The invention has the beneficial effects that:
the composite transition metal molecular sieve catalyst prepared by the invention has the advantages of simple preparation process, simple and easily obtained raw materials and low price; the VOCs can be directly decomposed into CO by utilizing the good catalytic activity of the transition metal and the developed pore structure of the molecular sieve material 2 And H 2 O, has no secondary pollution, is not easy to inactivate, can be widely applied to the field of VOCs waste gas catalytic combustion treatment in typical industries, and has good economical efficiency and use value.
Detailed Description
The present invention is described in detail below with reference to specific examples, but is not limited to the catalyst ratios discussed in the examples.
In the invention, the content of the active component refers to the percentage of the corresponding active component in the carrier weight calculated by the atomic mass of the transition metal or the rare earth metal in the active component precursor, and the mass ratio of the active component to the auxiliary agent refers to the atomic mass ratio, and the active component and the auxiliary agent are all fed according to the theoretical calculated amount.
Example 1
A composite transition metal molecular sieve catalyst and a preparation method thereof comprise the following steps:
first, 6.5mL 50% of Mn (NO) 3 ) 2 Solution, 3.775g Cu (NO) 3 ) 2 ·3H 2 Adding 43.5mL deionized water to O to obtain active component precursor solution, and adding 0.56g Ce (NO) 3 ) 3 ·6H 2 O, stirring and mixing 10g of ZSM-5 type molecular sieve in the solution, keeping the mixing temperature at 40 ℃, continuously dropwise adding an ammonia water solution in the stirring process, adjusting the pH value of the solution to 10-11, keeping the precipitation process for 30min, aging for 24h, washing the aged solution to be neutral by deionized water, filtering, drying and roasting the solid to obtain the composite catalyst; in the step, the drying temperature is 100 ℃, and the drying time is 24 hours; the roasting temperature is 500 ℃, and the roasting time is 4 hours; the content of the active components of the prepared catalyst is 20%, wherein the mass ratio of the active components is 1:1, the mass ratio of the active component to the auxiliary agent is 1:0.2.
example 2
A composite transition metal molecular sieve catalyst and a preparation method thereof comprise the following steps:
first 3.3mL 50% Mn (NO) 3 ) 2 Solution, 4.930g Co (NO) 3 ) 2 ·6H 2 Adding 46.7mL deionized water to O to obtain active component precursor solution, adding 0.29g Ce (NO) 3 ) 3 ·6H 2 O, stirring and mixing 10g of ZSM-5 type molecular sieve in the solution, keeping the mixing temperature at 50 ℃, continuously dripping an ammonia water solution in the stirring process, adjusting the pH value of the solution to 9-10, keeping the precipitation process for 60min, aging for 24h, washing the aged solution to be neutral by using deionized water, filtering, drying and roasting the solid to obtain the composite catalyst; in this step, drying is usedThe temperature is 105 ℃, and the drying time is 24 hours; the roasting temperature is 550 ℃, and the roasting time is 4 hours; the content of the active components of the prepared catalyst is 15%, wherein the mass ratio of the active components is 1:2, the mass ratio of the active component to the auxiliary agent is 1:0.2.
example 3
A composite transition metal molecular sieve catalyst and a preparation method thereof comprise the following steps:
first 2.9mL 50% of Mn (NO) 3 ) 2 Solution, 4.35g Co (NO) 3 ) 2 ·6H 2 Adding 47mL deionized water into O to obtain active component precursor solution, and adding 0.55g Ce (NO) 3 ) 3 ·6H 2 O, stirring and mixing 5g of ZSM-5 type molecular sieve and 5g of Na-Y type molecular sieve in the solution, keeping the mixing temperature at 50 ℃, and continuously dropwise adding 2mol/L Na in the stirring process 2 CO 3 Adjusting the pH value of the solution to 10-11, keeping the precipitation process for 40min, aging for 24h, washing the aged solution to be neutral by using deionized water, filtering, drying and roasting the solid to obtain the composite catalyst; in the step, the drying temperature is 100 ℃, and the drying time is 20 hours; the roasting temperature is 500 ℃, and the roasting time is 6 hours; the content of the active components of the prepared catalyst is 15%, wherein the mass ratio of the active components is 1:2, the mass ratio of the auxiliary agent to the active component is 1:0.4.
example 4
A composite transition metal molecular sieve catalyst and a preparation method thereof comprise the following steps:
first 2.7mL 50% Mn (NO) 3 ) 2 Solution, 3.89g Co (NO) 3 ) 2 ·6H 2 Adding 47.3mL deionized water to O to obtain active component precursor solution, adding 0.98g La (NO) 3 ) 3 After 1.5g of 6H2O polyethylene glycol is dissolved, 5g of ZSM-5 type molecular sieve and 5g of mordenite molecular sieve are stirred and mixed in the solution, the mixing temperature is kept at 50 ℃, and 2mol/L Na is continuously dripped in the stirring process 2 CO 3 Adjusting the pH value of the solution to 9-10, keeping the precipitation process for 60min, aging for 24h, washing the aged solution to be neutral by using deionized water, filtering, drying and roasting the solid to obtain the composite catalyst;in the step, the drying temperature is 110 ℃, and the drying time is 24 hours; the roasting temperature is 550 ℃, and the roasting time is 4 hours; the content of the active components of the prepared catalyst is 15%, wherein the mass ratio of the active components is 1:2, the mass ratio of the auxiliary agent to the active component is 1:0.8.
example 5
A composite transition metal molecular sieve catalyst and a preparation method thereof comprise the following steps:
first 3.6mL 50% Mn (NO) 3 ) 2 Solution, 1.37g Co (NO) 3 ) 2 ·6H 2 Adding 46.4mL deionized water to O to obtain active component precursor solution, adding 0.52g Ce (NO) 3 ) 3 ·6H 2 Dissolving 1.0g of polyethylene glycol, stirring and mixing 5g of Na-Y type molecular sieve and 5g of mordenite molecular sieve in the solution, keeping the mixing temperature at 50 ℃, and continuously dropwise adding 2mol/L Na in the stirring process 2 CO 3 Adjusting the pH value of the solution to 9-10, keeping the precipitation process for 30min, aging for 24h, washing the aged solution to be neutral by using deionized water, filtering, drying and roasting the solid to obtain the composite catalyst; in the step, the drying temperature is 110 ℃, and the drying time is 24 hours; the roasting temperature is 500 ℃, and the roasting time is 4 hours; the content of the active components of the prepared catalyst is 10%, wherein the mass ratio of the active components is 2:1, the mass ratio of the auxiliary agent to the active component is 1:0.6.
in other embodiments, the content of the active component in the catalyst is 5-25% of the weight of the carrier; the mass ratio of the active component to the auxiliary agent satisfies 1: (0.2-1).
In other embodiments, in the process of preparing the catalyst, the mixing and stirring time of the carrier is 30-60 min, the aging time is 12-24 h, the drying temperature is 100-150 ℃, the drying time is 12-24 h, and the roasting temperature is 500-600 ℃ to achieve the purpose of the invention.
Comparative example 1
First 2.9mL 50% of Mn (NO) 3 ) 2 Solution, 4.35g Co (NO) 3 ) 2 ·6H 2 Adding 47mL of deionized water into O to prepare active component precursor liquid, and adding 0.55g of Ce(NO 3 ) 3 ·6H 2 O, and then 10g of Al 2 O 3 After the solid particles are stirred and mixed in the solution, the mixing temperature is kept at 50 ℃, and 2mol/L Na is continuously dripped in the stirring process 2 CO 3 Adjusting the pH value of the solution to 10-11, keeping the precipitation process for 40min, aging for 24h, washing the aged solution to be neutral by using deionized water, filtering, drying and roasting the solid to obtain the composite catalyst; in the step, the drying temperature is 100 ℃, and the drying time is 20 hours; the roasting temperature is 500 ℃, and the roasting time is 6 hours; the content of the active components of the prepared catalyst is 15%, wherein the mass ratio of the active components is 1:2, the mass ratio of the auxiliary agent to the active component is 1:0.4.
this comparative example 1 compares with example 4 in that the catalyst support is replaced by Al from the molecular sieve 2 O 3 The other preparation methods were in accordance with example 4.
Comparative example 2
In comparison with example 3, in comparative example 2, NO auxiliary Ce (NO) was added during the preparation of the composite catalyst 3 ) 3 ·6H 2 O, other preparation procedures were consistent with example 3.
First 2.9mL 50% of Mn (NO) 3 ) 2 Solution, 4.35g Co (NO) 3 ) 2 ·6H 2 Adding 47mL of deionized water into O to prepare active component precursor liquid, stirring and mixing 5g of ZSM-5 type molecular sieve and 5g of Na-Y type molecular sieve in the solution, keeping the mixing temperature at 50 ℃, and continuously dropwise adding 2mol/L Na in the stirring process 2 CO 3 Adjusting the pH value of the solution to 10-11, keeping the precipitation process for 40min, aging for 24h, washing the aged solution to be neutral by using deionized water, filtering, drying and roasting the solid to obtain the composite catalyst; in the step, the drying temperature is 100 ℃, and the drying time is 20 hours; the roasting temperature is 500 ℃, and the roasting time is 6 hours; the content of the active components of the prepared catalyst is 15%, wherein the mass ratio of the active components is 1:2.
application test example:
to illustrate the effects of the present invention, examples 1 to 5 and comparative examples 1 to 2 were used as examples to conduct a single catalyst removal test.
The experimental conditions are as follows: in the experiment, a catalytic reactor adopts a quartz tube, the inner diameter of the reaction tube is 20mm, the length range of the reaction tube is 500mm, the length of a central heating zone is about 200mm, and the filling height of a catalyst is 20mm. An electric heating type tubular furnace is adopted for heating and temperature rise, and the reaction temperature is measured by a K-type thermocouple. VOCs gas is brought out by the bubbling bottle with air at a certain speed and is fully mixed with the other path of air in the mixing bottle to prepare VOCs gas with a certain concentration, and VOCs waste gas with different concentrations can be prepared by respectively controlling the flow through adjusting and controlling the mass flow controllers of the two paths of air. Organic gas enters a catalytic combustion reactor after being mixed in a mixing bottle, the organic gas is ignited by an electric heater, and after the organic gas to be reacted can recover heat generated by catalytic combustion reaction through a heat exchanger to maintain heat balance, qualitative and quantitative analysis is carried out on the organic gas before and after treatment through gas chromatography. The VOCs gas is toluene, the gas flow is 1L/min, the catalytic combustion airspeed is 10000-20000 h -1 . The results are shown in Table 1.
TABLE 1 catalyst VOCs removal efficiency
As can be seen from the results in Table 1, the light-off temperature of the composite transition metal molecular sieve catalysts prepared in examples 1-5 was about 225-275 deg.C, and the complete conversion temperature was below 300 deg.C. Comparative example 1 the light-off temperature was 275 ℃ and the complete conversion temperature was 350 ℃; comparative example 2 the light-off temperature was 250 ℃ and the complete conversion temperature was 325 ℃. The composite transition metal molecular sieve catalyst provided by the patent is better in catalytic performance of the molecular sieve as a carrier than an Al2O3 carrier, and meanwhile, the catalytic performance of the catalyst can be effectively improved by adding an auxiliary agent into the active component of the composite transition metal.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed.
Claims (10)
1. A composite transition metal molecular sieve catalyst comprising:
active components, auxiliaries, carriers and dispersants;
wherein:
the active component is one or more of nitrate, acetate and sulfate of transition metal elements;
the auxiliary agent is one or more of nitrate, acetate and sulfate of rare earth elements;
the carrier is any one or more of Y-type molecular sieve, ZSM-type molecular sieve and mordenite;
the dispersant is one or more of citric acid, polyethylene glycol, ethylene glycol and cetyl trimethyl ammonium bromide.
2. The composite transition metal molecular sieve catalyst of claim 1, wherein:
the transition metal element is any one or more of cobalt, copper, nickel, manganese, iron and chromium;
the rare earth element is one or the mixture of more than two of lanthanum and cerium.
3. The composite transition metal molecular sieve catalyst of claim 1, wherein:
the total weight of the active component and the auxiliary agent accounts for 5-25% of the carrier.
4. The composite transition metal molecular sieve catalyst of claim 3, wherein:
the mass ratio of the auxiliary agent to the active component is 1: (0.2-1).
5. A method for preparing the composite transition metal molecular sieve catalyst according to any one of claims 1 to 4, comprising:
adding water into the active component and the auxiliary agent to prepare an active component solution;
fully mixing the carrier and the dispersing agent in the active component solution, adjusting the pH value of the solution by using a precipitator, and carrying out coprecipitation;
washing, filtering, vacuum drying and roasting the precipitate to obtain the catalyst.
6. The production method according to claim 5, wherein:
the coprecipitation time of the carrier is 12-24 h;
the drying temperature is 100-150 ℃, and the drying time is 12-24 h;
the roasting temperature is 500-600 ℃, and the roasting time is 2-8 h.
7. The production method according to claim 5, wherein:
the precipitator is one or more of ammonia water, urea and sodium carbonate.
8. The production method according to claim 5, wherein:
the pH is adjusted to 7-11.
9. A composite transition metal molecular sieve catalyst prepared by the preparation method according to any one of claims 5 to 8.
10. The use of the composite transition metal molecular sieve catalyst of any of claims 1-4, 9 in low Wen Tuochu VOCs.
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