CN110302800B - Synthesis process of catalyst activated carbon composite material for decomposing dioxin - Google Patents
Synthesis process of catalyst activated carbon composite material for decomposing dioxin Download PDFInfo
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- CN110302800B CN110302800B CN201910360394.4A CN201910360394A CN110302800B CN 110302800 B CN110302800 B CN 110302800B CN 201910360394 A CN201910360394 A CN 201910360394A CN 110302800 B CN110302800 B CN 110302800B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 50
- 238000001035 drying Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008139 complexing agent Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 230000035515 penetration Effects 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 238000004056 waste incineration Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 18
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 239000002957 persistent organic pollutant Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010791 domestic waste Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002906 medical waste Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
Abstract
The invention discloses a synthesis process of a catalyst activated carbon composite material for decomposing dioxin, which comprises the following steps of A, crushing activated carbon, and sieving to obtain a product A; B. putting the product A into a container filled with concentrated sulfuric acid, introducing nitrogen into the bottom of the container, soaking, washing and drying to obtain a product B; C. adding alcohol and deionized water into product B and metal salt, and stirring to obtain product C; D. adding complexing agent into product C, ultrasonic penetrating, stirring, adjusting pH, and stirring to obtain product D; E. drying product D to obtain gel to obtain product E; F. under the protection of hydrogen, sintering the product E to obtain a product F; G. and removing impurities from the product F, washing and drying to obtain a finished product. According to the invention, the specific surface area of the modified activated carbon is increased, the catalyst is uniformly distributed in the activated carbon, the finished product is not easy to form pores and crack, the catalyst and the activated carbon have compact structures, the removal rate of the finished product on dioxin is higher and stable, and the service life of the finished product is prolonged.
Description
Technical Field
The invention relates to the technical field of catalyst composite materials for decomposing dioxin, in particular to a synthesis process of a catalyst active carbon composite material for decomposing dioxin.
Background
In 22 days 5 and 2001, stockholm sweden, more than 90 countries and regional representatives including china have officially signed the stockholm convention on persistent organic pollutants, which aims to reduce and eliminate persistent organic matters in the environment and protect human health and the environment from the harm of persistent organic pollutants, and the first 12 persistent organic pollutants represented by polyazabiphenyl, dioxin and the like become key targets of global chemical pollution control. China is the first contracting country of the "stockholm convention", and the convention formally takes effect on China in 2004 in 11 months and 11 days. According to the requirements of the convention, China compiles and completes the implementation plan that China fulfills < Stockholm convention about persistent organic pollutants > in 2007 as a general guide for the performance work of China. In the last 10 years, along with the acceleration of urbanization, the production amount of municipal domestic waste in China is greatly increased. According to the data provided by the national environmental sanitation society, the annual domestic garbage production of China is 440kg, the annual domestic garbage production of China reaches 1.5 hundred million t, the annual urban garbage production of China increases at the speed of 8-10%, the national annual garbage stock exceeds 60 hundred million t, and about 2/3 cities fall into the garbage surrounding city. Along with the rapid development of domestic waste incineration plants and waste incineration treatment capacity, the problem of dioxin discharged by domestic waste incineration plants also becomes the focus of public attention and debate. In provinces and markets with high popularization rate of waste incineration, such as Guangdong, Zhejiang, Jiangsu, Beijing and the like, public gathering events against waste incineration often occur. The dioxin emission control gradually becomes the key point in the waste incineration pollution control in China.
The traditional dioxin decomposition catalyst has limited improvement on the decomposition efficiency of dioxin and has higher requirements on reaction conditions such as temperature and the like. In recent years, the application of the activated carbon supported metal ion catalyst in degrading organic pollutants is increasing. The common preparation method of the active carbon-supported metal ion catalyst comprises the steps of firstly modifying active carbon, then fixedly supporting the metal ion catalyst in the modified active carbon by a sol-gel method, drying and sintering to obtain the catalyst-activated carbon composite material. In the preparation process of the existing catalyst active carbon composite material, the specific surface area of the modified active carbon is not large enough, the catalyst is not uniformly dispersed in the active carbon during sol-gel reaction, aggregates are easily generated, and the catalyst is easy to crack during drying, so that the performance of a finished product is not uniform, the removal rate of organic pollutants is not high enough and is not stable, and the service life of the finished product is shortened; during the sol-gel reaction, the connection between the catalyst and the activated carbon is not tight enough, pores are easy to form in the finished product prepared by sintering, and the service life of the finished product is shortened; when the gel is sintered, the temperature rise speed is improperly controlled, small air holes in the sol cannot be well eliminated, so that a sintered product is not compact enough and is easy to crack, and the service life of a finished product is shortened. Therefore, in the preparation of the existing catalyst activated carbon composite material, the specific surface area of the modified activated carbon is not large enough, the catalyst is unevenly distributed in the activated carbon, the finished product is easy to form pores and crack, the structure of the catalyst and the activated carbon is not compact enough, so that the removal rate of the finished product to organic pollutants is not high enough and unstable, and the service life of the finished product is short.
Disclosure of Invention
The invention aims to provide a synthesis process of a catalyst activated carbon composite material for decomposing dioxin. According to the invention, the specific surface area of the modified activated carbon is increased, the catalyst is uniformly distributed in the activated carbon, the finished product is not easy to form pores and crack, the catalyst and the activated carbon have compact structures, the removal rate of the finished product on dioxin is higher and stable, and the service life of the finished product is prolonged.
The technical scheme of the invention is as follows: the synthesis process of the catalyst-activated carbon composite material for decomposing dioxin comprises the following steps,
A. crushing the activated carbon, and sieving the crushed activated carbon with a 200-mesh and 300-mesh sieve to obtain a product A;
B. putting the product A into a container filled with concentrated sulfuric acid, introducing nitrogen into the bottom of the container, soaking for 2-3h, washing until the pH value is 6-7, and drying to obtain a product B;
C. taking 3-9 parts of the product B and 3-9 parts of metal salt, adding a mixed solution of 10-30 parts of alcohol and 30-60 parts of deionized water, and stirring to obtain a product C;
D. adding 4-10 parts of complexing agent into product C, performing ultrasonic penetration at 70-90 deg.C, stirring, adding dropwise ammonia water to adjust pH to 6.5-7, and stirring to obtain product D;
E. drying product D to obtain gel to obtain product E;
F. under the protection of hydrogen, sintering the E product at the temperature of 400-800 ℃ for 4-6h at the temperature rising speed of 2-5 ℃/min to obtain an F product;
G. and separating and removing impurities from the F product, washing and drying to obtain a finished product of the catalyst active carbon composite material.
In the synthesis process of the catalyst-activated carbon composite material for decomposing dioxin, in the step B, the flow rate of the nitrogen is 30-80 mL/min.
In the synthesis process of the catalyst activated carbon composite material for decomposing dioxin, in the step C, the metal salt is AgNO3、Mn(NO3)2And Fe (NO)3)3AgNO1-3 parts, Mn (NO)3)21-3 parts of Fe (NO)3)31-3 parts.
In the synthesis process of the catalyst-activated carbon composite material for decomposing dioxin, in the step C, the stirring time is 0.5-1.5h, the stirring temperature is 70-90 ℃, and the stirring speed is 400-450 rpm.
In the synthesis process of the catalyst-activated carbon composite material for decomposing dioxin, in the step D, the complexing agent is citric acid and ethylene glycol, 3.95-9.8 parts of citric acid and 0.05-0.2 part of ethylene glycol.
In the synthesis process of the catalyst activated carbon composite material for decomposing dioxin, in the step D, the ultrasonic penetration time is 5-15min, the ultrasonic frequency is 10-50KHZ, and the ultrasonic power density is 0.3-1KW/m3。
In the synthesis process of the catalyst activated carbon composite material for decomposing dioxin, the step D is to add a complexing agent into the product C, perform ultrasonic penetration for 5 to 15min at a constant temperature of between 70 and 90 ℃, wherein the ultrasonic frequency is between 10 and 50KHZ, and the ultrasonic power density is between 0.3 and 1KW/m3Stirring for 1.5-2.5h at 380-420rpm, adding ammonia water dropwise to adjust pH to 6.5-7, and stirring to obtain D product.
In the synthesis process of the catalyst-activated carbon composite material for decomposing dioxin, the step E is to dry the product D in a forced air drying oven at 70-90 ℃ for 5-7 hours to obtain the product E.
In the synthesis process of the catalyst activated carbon composite material for decomposing dioxin, the step F is to sinter the product E at the temperature of 400-800 ℃ for 3-4h and at the temperature of 700-800 ℃ for 1-2h under the protection of hydrogen to obtain the product F, wherein the heating rate is 2-5 ℃/min.
In the synthesis process of the catalyst-activated carbon composite for decomposing dioxin, in the step G, the separation is gravity separation.
Compared with the prior art, the method comprises the steps of crushing the activated carbon, sieving the crushed activated carbon by a 200-mesh and 300-mesh sieve, soaking the crushed activated carbon in concentrated sulfuric acid under the condition of introducing nitrogen, and introducing the nitrogen to ensure that the activated carbon is fully contacted with the concentrated sulfuric acid, so that the specific surface area of the modified activated carbon is greatly increased, the surface area for adsorbing dioxin is large enough, and enough pores can be used for immobilizing the metal ion catalyst; the proportion of the product B, the metal salt and the complexing agent is proper, metal ions can be fully immobilized in the modified activated carbon under the conditions of reaction temperature and pH value, the sol performance is stable, the prepared catalyst has a remarkable catalytic effect, the catalyst is used for removing dioxin in waste incineration tail gas, the removal rate is more than 99.6 percent, and the proportion of deionized water and alcohol is proper, so that the vapor pressure is not too high when the sol is dried, and the sol is not cracked when the sol is dried; in the step D of the invention, the metal ions are distributed more uniformly by ultrasonic penetration, so that the metal ions are fully and fixedly loaded in the activated carbon, the generation of aggregates is avoided, the cracking probability of the sol during drying and sintering is reduced, the finished product has uniform texture, and the removal rate of the finished product to dioxin is higher and more stable; in the step F of the invention, the heating speed is proper, and small air holes in the product E can be eliminated slowly, so that the finished product is more compact and does not crack or form fine holes. According to the invention, the specific surface area of the modified activated carbon is increased, the catalyst is uniformly distributed in the activated carbon, the finished product is not easy to form pores and crack, the catalyst and the activated carbon have compact structures, the removal rate of the finished product on dioxin is higher and stable, and the service life of the finished product is prolonged.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1.
The synthesis process of the catalyst-activated carbon composite material for decomposing dioxin comprises the following steps,
A. crushing activated carbon (the activated carbon is washed and dried by deionized water), and sieving with a 200-mesh sieve to obtain a product A;
B. putting the product A into a container filled with concentrated sulfuric acid, introducing nitrogen into the bottom of the container, soaking for 3h at the flow rate of 30mL/min, washing until the pH value is 6.5, and drying to obtain a product B;
C. taking 6 parts of B product and 1 part of AgNO31 part of Mn (NO)3)2And 2 parts of Fe (NO)3)3Adding a mixed solution of 10 parts of alcohol and 30 parts of deionized water, and stirring for 0.5h at the stirring temperature of 70 ℃ and the stirring speed of 400rpm to obtain a product C;
D. adding complexing agent into product C, wherein the complexing agent is citric acid and ethylene glycol, the citric acid is 3.95 parts, the ethylene glycol is 0.05 part, and performing ultrasonic penetration for 5min at a constant temperature of 70 ℃, the ultrasonic frequency is 10KHZ, and the ultrasonic power density is 0.3KW/m3Stirring for 1.5h at the stirring speed of 380rpm, dropwise adding ammonia water to adjust the pH value to 6.6,stirring to obtain D product;
E. drying the product D in a forced air drying oven at 70 deg.C for 6.5h to obtain product E;
F. under the protection of hydrogen, placing the product E in a tube furnace, sintering at 400 ℃ for 3h, and sintering at 700 ℃ for 1h, wherein the heating rate is 2 ℃/min, and obtaining a product F;
G. and (4) performing gravity separation and impurity removal on the product F, washing the product F with deionized water until the pH value is 7, and drying the product F to obtain a finished product of the catalyst activated carbon composite material for decomposing dioxin.
The catalyst-activated carbon composite material for decomposing dioxin is used for decomposing dioxin in waste incineration tail gas: the prepared catalyst active carbon composite material for decomposing dioxin is filled in a tail gas discharge pipeline of a waste incineration device, and the removal rate of the dioxin in the tail gas reaches 99.78%.
Example 2.
The synthesis process of the catalyst-activated carbon composite material for decomposing dioxin comprises the following steps,
A. crushing activated carbon (the activated carbon is washed and dried by deionized water), and sieving with a 300-mesh sieve to obtain a product A;
B. putting the product A into a container filled with concentrated sulfuric acid, introducing nitrogen into the bottom of the container, soaking for 3h at the flow rate of the nitrogen of 60mL/min, washing until the pH value is 7, and drying to obtain a product B;
C. taking 3 parts of B product and 1 part of AgNO31 part of Mn (NO)3)2And 1 part of Fe (NO)3)3Adding a mixed solution of 15 parts of alcohol and 30 parts of deionized water, and stirring for 1.5 hours at the stirring temperature of 90 ℃ and the stirring speed of 450rpm to obtain a product C;
D. adding complexing agent into product C, wherein the complexing agent is citric acid and ethylene glycol, the citric acid is 3.95 parts, the ethylene glycol is 0.05 part, performing ultrasonic penetration for 15min at 90 ℃ constant temperature, the ultrasonic frequency is 50KHZ, and the ultrasonic power density is 1KW/m3Stirring for 2.5h at the stirring speed of 420rpm, dropwise adding ammonia water to adjust the pH value to 7, and stirring until the solution is in a sol state to obtain a product D;
E. and drying the product D in a forced air drying oven at 90 ℃ for 7h to obtain a product E.
F. Under the protection of hydrogen, placing the product E in a tube furnace, sintering at 600 ℃ for 3.5h, and sintering at 800 ℃ for 2h, wherein the heating rate is 5 ℃/min, and obtaining a product F;
G. and (4) performing gravity separation and impurity removal on the product F, washing the product F with deionized water until the pH value is 7, and drying the product F to obtain a finished product of the catalyst activated carbon composite material for decomposing dioxin.
The catalyst-activated carbon composite material for decomposing dioxin is used for decomposing dioxin in waste incineration tail gas: the prepared catalyst active carbon composite material for decomposing dioxin is filled in a tail gas discharge pipeline of a waste incineration device, and the removal rate of the dioxin in the tail gas reaches 99.69%.
Example 3.
The synthesis process of the catalyst-activated carbon composite material for decomposing dioxin comprises the following steps,
A. crushing activated carbon (the activated carbon is washed and dried by deionized water), and sieving with a 250-mesh sieve to obtain a product A;
B. putting the product A into a container filled with concentrated sulfuric acid, introducing nitrogen into the bottom of the container, soaking for 3h at the flow rate of 80mL/min, washing until the pH value is 7, and drying to obtain a product B;
C. taking 7 parts of B product and 2 parts of AgNO32 parts of Mn (NO)3)2And 2 parts of Fe (NO)3)3Adding a mixed solution of 20 parts of alcohol and 45 parts of deionized water, and stirring for 1 hour at the stirring temperature of 90 ℃ and the stirring speed of 450rpm to obtain a product C;
D. adding complexing agent into product C, wherein the complexing agent is citric acid and ethylene glycol, the citric acid is 7 parts, the ethylene glycol is 0.12 part, performing ultrasonic penetration for 15min at 90 ℃ constant temperature, the ultrasonic frequency is 30KHZ, and the ultrasonic power density is 0.7KW/m3Stirring for 2h at the stirring speed of 400rpm, dropwise adding ammonia water to adjust the pH value to 7, and stirring until the solution is in a sol state to obtain a product D;
E. and drying the product D in a forced air drying oven at 90 ℃ for 7h to obtain a product E.
F. Under the protection of hydrogen, placing the product E in a tube furnace, sintering at 500 ℃ for 3.5h, sintering at 800 ℃ for 2h, and heating at a speed of 3 ℃/min to obtain a product F;
G. and (4) performing gravity separation and impurity removal on the product F, washing the product F with deionized water until the pH value is 7, and drying the product F to obtain a finished product of the catalyst activated carbon composite material for decomposing dioxin.
The catalyst-activated carbon composite material for decomposing dioxin is used for decomposing dioxin in waste incineration tail gas: the prepared catalyst active carbon composite material for decomposing dioxin is filled in a tail gas discharge pipeline of a waste incineration device, and the removal rate of the dioxin in the tail gas reaches 99.85 percent.
Example 4.
The synthesis process of the catalyst-activated carbon composite material for decomposing dioxin comprises the following steps,
A. crushing activated carbon (the activated carbon is washed and dried by deionized water), and sieving with a 220-mesh sieve to obtain a product A;
B. putting the product A into a container filled with concentrated sulfuric acid, introducing nitrogen into the bottom of the container, soaking for 3h at the flow rate of the nitrogen of 60mL/min, washing until the pH value is 7, and drying to obtain a product B;
C. taking 9 parts of B product and 3 parts of AgNO33 parts of Mn (NO)3)2And 3 parts of Fe (NO)3)3Adding a mixed solution of 30 parts of alcohol and 60 parts of deionized water, and stirring for 1 hour at the stirring temperature of 90 ℃ and the stirring speed of 430rpm to obtain a product C;
D. adding complexing agent into product C, wherein the complexing agent is citric acid and ethylene glycol, the citric acid is 10 parts, the ethylene glycol is 0.2 part, performing ultrasonic penetration for 15min at 90 ℃ constant temperature, the ultrasonic frequency is 30KHZ, and the ultrasonic power density is 0.8KW/m3Stirring for 2h at the stirring speed of 400rpm, dropwise adding ammonia water to adjust the pH value to 7, and stirring until the solution is in a sol state to obtain a product D;
E. and drying the product D in a forced air drying oven at 90 ℃ for 6h to obtain a product E.
F. Under the protection of hydrogen, placing the product E in a tube furnace, sintering at 600 ℃ for 4h, sintering at 800 ℃ for 2h, and heating at the speed of 4 ℃/min to obtain a product F;
G. and (4) performing gravity separation and impurity removal on the product F, washing the product F with deionized water until the pH value is 7, and drying the product F to obtain a finished product of the catalyst activated carbon composite material for decomposing dioxin.
The catalyst-activated carbon composite material for decomposing dioxin is used for decomposing dioxin in waste incineration tail gas: the prepared catalyst active carbon composite material for decomposing dioxin is filled in a tail gas discharge pipeline of a waste incineration device, and the removal rate of the dioxin in the tail gas reaches 99.77 percent.
Example 5.
The synthesis process of the catalyst-activated carbon composite material for decomposing dioxin comprises the following steps,
A. crushing activated carbon (the activated carbon is washed and dried by deionized water), and sieving by a 260-mesh sieve to obtain a product A;
B. putting the product A into a container filled with concentrated sulfuric acid, introducing nitrogen into the bottom of the container, soaking for 2.5h at the flow rate of 55mL/min, washing until the pH value is 7, and drying to obtain a product B;
C. taking 5 parts of B product and 1 part of AgNO31 part of Mn (NO)3)2And 1 part of Fe (NO)3)3Adding a mixed solution of 20 parts of alcohol and 40 parts of deionized water, and stirring for 1 hour at the stirring temperature of 80 ℃ and the stirring speed of 430rpm to obtain a product C;
D. adding complexing agent into product C, wherein the complexing agent is citric acid and ethylene glycol, the citric acid is 6 parts, the ethylene glycol is 0.1 part, performing ultrasonic penetration for 10min at 80 ℃ for constant temperature, the ultrasonic frequency is 30KHZ, and the ultrasonic power density is 0.6KW/m3Stirring for 2h at the stirring speed of 400rpm, dropwise adding ammonia water to adjust the pH value to 7, and stirring until the solution is in a sol state to obtain a product D;
E. and drying the product D in a forced air drying oven at 80 ℃ for 6h to obtain a product E.
F. Under the protection of hydrogen, placing the product E in a tube furnace, sintering at 500 ℃ for 3.5h, and sintering at 750 ℃ for 1.5h, wherein the heating rate is 3 ℃/min, and obtaining a product F;
G. and (4) performing gravity separation and impurity removal on the product F, washing the product F with deionized water until the pH value is 7, and drying the product F to obtain a finished product of the catalyst activated carbon composite material.
The catalyst-activated carbon composite material for decomposing dioxin is used for decomposing dioxin in waste incineration tail gas: the prepared catalyst active carbon composite material for decomposing dioxin is filled in a tail gas discharge pipeline of a waste incineration device, and the removal rate of the dioxin in the tail gas reaches 99.89%.
In examples 1 to 5, stirring was carried out using a magnetic stirrer.
Comparative example. The waste incineration device without the catalyst activated carbon composite material for decomposing dioxin in the tail gas pipeline was used for testing the content of dioxin (ng TEQ/m) in 9 batches of waste incineration tail gas3) The measured dioxin content is shown in table 1:
the garbage samples in the embodiment and the comparative example of the invention are mixed garbage consisting of domestic garbage and medical waste garbage, the domestic garbage and the medical waste garbage in the garbage samples are fully mixed, and the samples are uniform. The waste incineration amount and incineration conditions in the comparative example and the examples were the same as the dioxin sampling conditions.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. The synthesis process of the catalyst active carbon composite material for decomposing dioxin is characterized by comprising the following steps of: comprises the following steps of (a) carrying out,
A. crushing the activated carbon, and sieving the crushed activated carbon with a 200-mesh and 300-mesh sieve to obtain a product A;
B. putting the product A into a container filled with concentrated sulfuric acid, introducing nitrogen into the bottom of the container, soaking for 2-3h at the flow rate of 30-80mL/min, washing until the pH value is 6-7, and drying to obtain a product B;
C. taking 3-9 parts of B product and 3-9 parts of metal salt, wherein the metal salt is AgNO3、Mn(NO3)2And Fe (NO)3)3，AgNO31-3 parts of Mn (NO)3)21-3 parts of Fe (NO)3)31-3 parts of alcohol and 30-60 parts of deionized water, and stirring to obtain a product C;
D. adding 4-10 parts of complexing agent into the product C, wherein the complexing agent is citric acid and glycol, the citric acid is 3.95-9.8 parts, the glycol is 0.05-0.2 part, and ultrasonic penetration is carried out at a constant temperature of 70-90 ℃ for 5-15min at an ultrasonic frequency of 10-50KHZ and an ultrasonic power density of 0.3-1KW/m3Stirring, adding dropwise ammonia water to adjust pH to 6.5-7, and stirring to obtain D product;
E. drying product D to obtain gel to obtain product E;
F. under the protection of hydrogen, sintering the E product at the temperature of 400-800 ℃ for 4-6h at the temperature rising speed of 2-5 ℃/min to obtain an F product;
G. and separating and removing impurities from the F product, washing and drying to obtain a finished product of the catalyst active carbon composite material.
2. The synthesis process of the catalyst-activated carbon composite for decomposition of dioxin according to claim 1, characterized by comprising: in the step C, the stirring time is 0.5-1.5h, the stirring temperature is 70-90 ℃, and the stirring speed is 400-450 rpm.
3. The synthesis process of the catalyst-activated carbon composite for decomposition of dioxin according to claim 1, characterized by comprising: d, adding a complexing agent into the product C, and performing ultrasonic penetration for 5-15min at a constant temperature of 70-90 ℃, wherein the ultrasonic frequency is 10-50KHZ, and the ultrasonic power density is 0.3-1KW/m3Stirring for 1.5-2.5h at 380-420rpm, adding ammonia water dropwise to adjust pH to 6.5-7, and stirring to obtain D product.
4. The synthesis process of the catalyst-activated carbon composite for decomposition of dioxin according to claim 1, characterized by comprising: and E, drying the product D in a forced air drying oven at 70-90 ℃ for 5-7h to obtain a product E.
5. The synthesis process of the catalyst-activated carbon composite for decomposition of dioxin according to claim 1, characterized by comprising: and the step F is to sinter the E product at the temperature of 400-800 ℃ for 3-4h and at the temperature of 700-800 ℃ for 1-2h under the protection of hydrogen to obtain the F product, wherein the heating speed is 2-5 ℃/min.
6. The synthesis process of the catalyst-activated carbon composite for decomposition of dioxin according to claim 1, characterized by comprising: in step G, the separation is gravity separation.
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