CN109225207B - Catalyst for removing dioxin and preparation method thereof - Google Patents
Catalyst for removing dioxin and preparation method thereof Download PDFInfo
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
Abstract
The invention discloses a catalyst for removing dioxin, which belongs to the technical field of catalysts and comprises a carrier TiO2The active ingredient is V2O5、WO3、CeO2And MnO2The contents of the components are as follows according to parts by weight: 70-90 parts of TiO21.0 to 5.0 parts of SiO21.0 to 5.0 parts of V2O50.1 to 3.0 parts of MnO20.1 to 3.0 parts of CeO22.0 to 8.0 parts of WO3And a portion of the auxiliary material; the auxiliary material comprises the following components of a binder, a cosolvent, a pore-forming agent, a structural auxiliary agent, an acid solution, an alkali liquor, monoethanolamine and deionized water. By adopting the technical scheme, the catalyst has V2O5、WO3、CeO2And MnO2The catalyst promoter substance forms a multi-element metal atom cluster, reduces the activation energy required by the reaction, and improves the dioxin removal effect; and secondly, the silicon dioxide accounts for 1.0-5.0% of the total amount of the catalyst, so that the catalytic effect of the catalyst can be kept in a better state, and the mechanical properties of the catalyst, such as wear resistance, compressive strength and the like, are enhanced.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for removing dioxin and a preparation method thereof.
Background
Dioxin, also called dioxin, is a colorless, tasteless, and severely toxic fat-soluble substance, and the benzene ring substituted by 2 chlorine atoms connected by 1 oxygen atom is polychlorinated dibenzofuran (PCDFs). Each benzene ring can be substituted with 1-4 chlorine atoms to form a plurality of isomers, wherein 75 isomers of PCDDs exist, and 135 isomers of PCDFs exist.
Dioxins can bind to aromatic hydrocarbon receptors and lead to a general term for a large class of substances that produce various biochemical changes. The method mainly comprises the following steps: polychlorinated dibenzodioxins, polychlorinated dibenzofurans and coplanar polychlorinated biphenyls, among which most studied are also the most typical and most toxic 2, 3, 7, 8 tetrachlorodibenzo-p-dioxins, whose toxicity is 1000 times that of potassium cyanide (KCN), are known as the most toxic poisons on the earth.
Microorganisms and hydrolysis in nature have little influence on the molecular structure of dioxin, so that the dioxin in the environment is difficult to naturally degrade and eliminate. Experiments prove that dioxin can damage various organs and systems and stays for a long time once entering the human body because of chemical stability and easy absorption by adipose tissues and is accumulated in the body for a long time, and possibly causes cancer through an indirect physiological route. Their half-life in vivo is estimated to be 7 to 11 years. In addition, it also readily forms strong bonds with soil or other particulate matter, is extremely difficult to remove once contaminated, is highly durable and cumulative, and can pose a serious hazard to humans through the scale-up of the food chain.
The method mainly comprises an active carbon adsorption technology and catalytic oxidation decomposition aiming at the treatment technology of dioxin substances in flue gas, wherein the active carbon adsorption technology is used for removing the dioxin in the flue gas by utilizing the adsorption action of active carbon, and the method is not decomposed and destroyed, so that the subsequent treatment of fly ash rich in high-concentration dioxin is required. For example: secondary high-temperature incineration is carried out, and secondary pollution is easily caused if the treatment is improper.
The catalytic oxidative decomposition is to decompose dioxin pollutants into CO2, H2O, and inorganic small molecules such as HCl, so as to achieve the purpose of complete degradation, and the core of developing the catalytic oxidative decomposition technology is a catalyst, so how to prepare the catalyst capable of degrading dioxin pollutants is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a catalyst for removing dioxin, which takes V2O5, WO3, CeO2 and MnO2 as active substances to form a multi-element metal atom cluster, reduces the activation energy required by reaction, effectively improves the effect of removing dioxin, adjusts the proportion of SiO2, and strengthens the mechanical properties of the catalyst such as wear resistance, compressive strength and the like. In addition, the preparation method is simple and suitable for large-scale production.
The technical purpose of the invention is realized by the following technical scheme:
a catalyst for removing dioxin contains TiO as carrier2The active ingredient is V2O5、WO3、CeO2And MnO2The contents of the components are as follows according to parts by weight: 70-90 parts of TiO21.0 to 5.0 parts of SiO21.0 to 5.0 parts of V2O50.1 to 3.0 parts of MnO20.1 to 3.0 parts of CeO22.0 to 8.0 parts of WO3And a portion of the auxiliary material; the auxiliary material comprises the following components of a binder, a cosolvent, a pore-forming agent, a structural auxiliary agent, an acid solution, an alkali liquor, monoethanolamine and deionized water.
By adopting the technical scheme, the catalyst has V2O5、WO3、CeO2And MnO2The catalyst promoter substance forms a multi-element metal atom cluster, reduces the activation energy required by the reaction, and improves the dioxin removal effect; and secondly, the silicon dioxide accounts for 1.0-5.0% of the total amount of the catalyst, so that the catalytic effect of the catalyst can be kept in a better state, and the mechanical properties of the catalyst, such as wear resistance, compressive strength and the like, are enhanced.
Preferably, the TiO is2Is anatase titanium dioxide.
By adopting the technical scheme, the anatase titanium dioxide is selected as the catalyst carrier, so that the weather resistance of the catalyst can be effectively enhanced, and the storage time of the catalyst can be prolonged.
Preferably, the binder is a mixture of carboxymethylcellulose and ethylene oxide.
Preferably, the cosolvent is a mixture of stearic acid and ethylene bis-fatty acid amide.
By adopting the technical scheme, the stearic acid and the ethylene bis-fatty acid amide can effectively improve the mutual mixing effect of the substances. Meanwhile, the ethylene bis fatty acid amide also has a polar group structure combined with partial polar groups on the surfaces of the glass fiber, the carrier and the cocatalyst. The ethylene bis fatty acid amide forms similar anchoring nodes among the glass fiber, the carrier and the cocatalyst, improves the bonding state among the glass fiber, the carrier and the cocatalyst, and further improves the dispersibility of the glass fiber in the carrier and the cocatalyst. Thus, it is also advantageous to enhance the structural strength of the catalyst.
Preferably, the pore-forming agent is one of wood pulp, activated carbon and paper pulp cotton.
Preferably, the structural assistant is glass fiber.
Preferably, the acid solution is one of lactic acid and oxalic acid.
Preferably, the alkali liquor is a mixture of ammonia water and calcium hydroxide.
By adopting the technical scheme, because the stearic acid contains fatty acid radical ions which can react with Ca in the solution of calcium hydroxide2+、CaOH+The plasma reaction generates fatty acid calcium precipitate, and finally the fatty acid calcium precipitate is coated on the surface of the titanium dioxide particles. Meanwhile, the fatty acid calcium has stronger cohesiveness, so that other materials can be better attached to the carrier, and the structural strength of the catalyst is effectively improved. The ammonia water and the calcium hydroxide are used together, so that the alkalinity of the alkali liquor can be ensured, and the ammonia water can be removed in an ammonia gas manner in the calcining process, thereby ensuring the mass ratio of the carrier to the cocatalyst.
A preparation method of a catalyst for removing dioxin comprises the following steps,
preparation of active solution:
mixing and dissolving ammonium metavanadate and monoethanolamine in deionized water at 85-95 ℃ according to the mass ratio of 1:1, and storing at constant temperature of 40-60 ℃ for later use;
mixing operation:
the method comprises the following steps: uniformly mixing titanium dioxide serving as a carrier of a catalyst, silicon dioxide, ammonium metatungstate serving as a precursor of a catalysis-assisting component, cerium nitrate and manganese oxalate with a cosolvent, an acid solution and an alkali solution to obtain a first mixture;
step two: adding the prepared active solution, the pore-forming aid and the structural aid into the mixture I, and uniformly mixing to obtain a mixture II;
step three: adding a binder into the mixture II, and uniformly mixing to finish the preparation of the blank;
step four: aging the prepared blank for 12-36 h;
step five: filtering and molding the aged blank to obtain a honeycomb catalyst blank;
step six: drying the catalyst blank, gradually increasing the drying temperature from 20 ℃ to 90 ℃, reducing the humidity from 100% to 20%, and drying for 200-400 h;
step seven: and coating the dried catalyst blank with heat insulation cotton, and then putting the coated catalyst blank into a kiln for calcination to prepare the finished catalyst, wherein the calcination highest temperature is 650 ℃, and the total time is 30-50 h.
By adopting the technical scheme, the blank is aged, so that the substances in the blank can be uniformly mixed and fully reacted. The blank body can be densified in the calcining process, the local temperature of the blank body can be gradually reduced in the process, and the heat preservation cotton can play a heat preservation role in the blank body, so that the blank body can be completely sintered.
Furthermore, the ammonium metatungstate is directly added into the mixture, so that the content of the ammonium metatungstate in the material can be increased, and the quality of the catalyst is improved.
Preferably, the temperature of the calcination in step seven is gradually increased from normal temperature to the maximum temperature in 1/2 total time, and then gradually falls back to the normal temperature state in the remaining 1/2 total time.
By adopting the technical scheme, the calcination temperature of the catalyst is changed in a parabolic shape, so that compared with the situation that the temperature is rapidly increased, the problem that after the body surface of the blank body is solidified, moisture or volatile substances exist in the catalyst, the surface solidified part is cracked, and the quality of the finished product of the catalyst is further influenced can be avoided.
In conclusion, the invention has the following beneficial effects:
1. the invention uses V2O5、WO3、CeO2And MnO2As an active substance, a multi-element metal atom cluster is formed, the activation energy required by the reaction is reduced, and the efficiency of removing dioxin is improved;
2. in the invention, SiO is regulated2The proportion of (A) enhances the mechanical properties of the catalyst, such as abrasion resistance, compressive strength and the like;
3. during calcination, the blank is coated with heat-insulating cotton, so that the blank can be uniformly heated inside, and the probability of cracking of a finished product can be avoided.
Detailed Description
The first embodiment is as follows:
a preparation method of a dioxin removing catalyst comprises the following steps:
1) preparation of active liquid:
active solution: heating 100L of deionized water to 60-80 ℃, stirring, adding 1.28kg of monoethanolamine, continuing to heat, adding 1.28kg of ammonium metavanadate when the temperature reaches 85-95 ℃, then preserving the heat at 95 ℃ for 30min to ensure that the ammonium metavanadate is completely dissolved, and cooling to 40-60 ℃ for heat preservation for later use.
2) Mixing operation:
the first step is as follows: 70.00kg of anatase titanium dioxide, 1.00kg of silicon dioxide and a promoter precursor of 2.14kg of ammonium metatungstate, 0.25kg of cerium nitrate and 0.16kg of manganese oxalate are weighed and added into a mixing roll for dry mixing uniformly.
The second step is that: and sequentially adding 0.25kg of stearic acid, 0.25kg of ethylene bis fatty acid amide, 0.65kg of lactic acid, 10L of mixed solution of ammonia water and calcium hydroxide and 50L of deionized water, and mixing to obtain a mixture I.
The third step: and adding 0.30kg of wood pulp, 3.3kg of glass fiber and all prepared active solutions into the first mixed material in a mixing roll, and uniformly mixing to obtain a second mixed material.
The fourth step: and when the temperature of the mixture II is reduced to 55-65 ℃, adding 1.0kg of carboxymethyl cellulose and 1.0kg of ethylene oxide, and uniformly mixing to obtain a blank.
The fifth step: and sealing and preserving the blank in an environment with the temperature of 35-45 ℃ and the humidity of 45-65% for ageing for 12 hours.
And a sixth step: and filtering and forming the aged blank to obtain a honeycomb catalyst blank.
The seventh step: drying the catalyst embryo body, wherein the drying temperature is gradually increased from 20 ℃ to 90 ℃, the humidity is decreased from 100% to 20%, and the drying time is 200 h.
Eighth step: and (3) coating the dried catalyst blank with heat insulation cotton, putting the coated catalyst blank into a kiln for calcination to prepare a finished catalyst, gradually raising the calcination temperature from the normal temperature to the highest temperature of 550 ℃ within the total time of 1/2, and gradually falling back to the normal temperature within the remaining total time of 1/2 for 30 hours.
Wherein the mass ratio of the ammonia water to the calcium hydroxide is 1:1, and the pH value of the mixed liquid of the ammonia water and the calcium hydroxide is 9.
Example two:
a preparation method of a dioxin removing catalyst comprises the following steps:
1) preparation of active liquid:
active solution: heating 100L of deionized water to 60-80 ℃, stirring, adding 6.43kg of monoethanolamine, continuing to heat, adding 6.43kg of ammonium metavanadate when the temperature reaches 85-95 ℃, then preserving the heat at 95 ℃ for 30min to ensure that the ammonium metavanadate is completely dissolved, and cooling to 40-60 ℃ for heat preservation for later use.
2) Mixing operation:
the first step is as follows: 90.00kg of anatase titanium dioxide, 5.00kg of silicon dioxide and a promoter precursor of 8.55kg of ammonium metatungstate, 7.57kg of cerium nitrate and 4.93kg of manganese oxalate are weighed and added into a mixing roll for dry mixing uniformly.
The second step is that: 0.75kg of stearic acid, 0.75kg of ethylene bis fatty acid amide, 1.95kg of lactic acid, 20L of mixed solution of ammonia water and calcium hydroxide and 100L of deionized water are sequentially added and mixed to obtain a mixture I.
The third step: and adding 0.90 of activated carbon, 10.00kg of glass fiber and all prepared active solutions into the first mixed material, and uniformly mixing to obtain a second mixed material.
The fourth step: and when the temperature of the mixture II is reduced to 55-65 ℃, adding 3.00kg of carboxymethyl cellulose and 3.00kg of ethylene oxide, and uniformly mixing to obtain a blank.
The fifth step: and sealing and preserving the blank in an environment with the temperature of 35-45 ℃ and the humidity of 45-65% for ageing for 12 hours.
And a sixth step: and filtering and forming the aged blank to obtain a honeycomb catalyst blank.
The seventh step: and drying the catalyst embryo body, wherein the drying temperature is gradually increased from 20 ℃ to 90 ℃, the humidity is decreased from 100% to 20%, and the drying time is 400 h.
Eighth step: and (3) coating the dried catalyst blank with heat insulation cotton, putting the coated catalyst blank into a kiln for calcination to prepare a finished catalyst, wherein the calcination temperature is gradually increased from the normal temperature to the highest temperature of 650 ℃ within 1/2 total time, and then gradually falls back to the normal temperature state within the remaining 1/2 total time for 50 hours.
Wherein the mass ratio of the ammonia water to the calcium hydroxide is 1:1, and the pH value of the mixed liquid of the ammonia water and the calcium hydroxide is 9.
Example three:
a preparation method of a dioxin removing catalyst comprises the following steps:
1) preparation of active liquid:
active solution: heating 100L of deionized water to 60-80 ℃, stirring, adding 3.86kg of monoethanolamine, continuing to heat, adding 3.86kg of ammonium metavanadate when the temperature reaches 85-95 ℃, then preserving the heat at 95 ℃ for 30min to ensure that the ammonium metavanadate is completely dissolved, and cooling to 40-60 ℃ for heat preservation for later use.
2) Mixing operation:
the first step is as follows: weighing 80.00kg of anatase titanium dioxide, 3.00kg of silicon dioxide and a promoter precursor of 5.34kg of ammonium metatungstate, 3.78kg of cerium nitrate and 2.47kg of manganese oxalate, adding into a mixing roll, and carrying out dry mixing uniformly.
The second step is that: 0.50kg of stearic acid, 0.50kg of ethylene bis fatty acid amide, 1.30kg of lactic acid, 15L of mixed solution of ammonia water and calcium hydroxide and 75L of deionized water are sequentially added and mixed to obtain a mixture I.
The third step: and adding 0.60kg of paper pulp cotton, 6.60kg of glass fiber and all prepared active solutions into the mixed material I, and uniformly mixing to obtain a mixed material II.
The fourth step: and when the temperature of the mixture II is reduced to 55-65 ℃, adding 2.00kg of carboxymethyl cellulose and 2.00kg of ethylene oxide, and uniformly mixing to obtain a blank.
The fifth step: and sealing and preserving the blank in an environment with the temperature of 35-45 ℃ and the humidity of 45-65% for ageing for 12 hours.
The sixth step: and filtering and forming the aged blank to obtain a honeycomb catalyst blank.
The seventh step: and drying the catalyst embryo body, wherein the drying temperature is gradually increased from 20 ℃ to 90 ℃, the humidity is decreased from 100% to 20%, and the drying time is 300 h.
Eighth step: and (3) coating the dried catalyst blank with heat insulation cotton, putting the coated catalyst blank into a kiln for calcination to prepare a finished catalyst, gradually raising the calcination temperature from the normal temperature to the maximum temperature of 600 ℃ within the total time of 1/2, and gradually falling back to the normal temperature state within the remaining total time of 1/2 for 40 hours.
Wherein the mass ratio of the ammonia water to the calcium hydroxide is 1:1, and the pH value of the mixed liquid of the ammonia water and the calcium hydroxide is 9.
Example four:
a preparation method of a dioxin removing catalyst comprises the following steps:
1) preparation of active liquid:
active solution: heating 100L of deionized water to 60-80 ℃, stirring, adding 1.28kg of monoethanolamine, continuing to heat, adding 1.28kg of ammonium metavanadate when the temperature reaches 85-95 ℃, then preserving the heat at 95 ℃ for 30min to ensure that the ammonium metavanadate is completely dissolved, and cooling to 40-60 ℃ for heat preservation for later use.
2) Mixing operation:
the first step is as follows: weighing 80.00kg of anatase titanium dioxide, 5.00kg of silicon dioxide and promoter precursor 5.34kg of ammonium metatungstate, 7.57kg of cerium nitrate and 0.16kg of manganese oxalate, adding into a mixing roll, and carrying out dry mixing uniformly.
The second step is that: and sequentially adding 0.50kg of stearic acid, 0.50kg of ethylene bis-fatty acid amide, 1.30kg of oxalic acid, 10L of mixed solution of ammonia water and calcium hydroxide and 50L of deionized water, and mixing to obtain a mixture I.
The third step: and adding 0.60kg of paper pulp cotton, 3.30kg of glass fiber and all prepared active solutions into the mixed material I, and uniformly mixing to obtain a mixed material II.
The fourth step: and when the temperature of the mixture II is reduced to 55-65 ℃, adding 1.00kg of carboxymethyl cellulose and 1.00kg of ethylene oxide, and uniformly mixing to obtain a blank.
The fifth step: and sealing and preserving the blank in an environment with the temperature of 35-45 ℃ and the humidity of 45-65% for ageing for 12 hours.
And a sixth step: and filtering and forming the aged blank to obtain a honeycomb catalyst blank.
The seventh step: and drying the catalyst embryo body, wherein the drying temperature is gradually increased from 20 ℃ to 90 ℃, the humidity is decreased from 100% to 20%, and the drying time is 400 h.
The eighth step: and (3) coating the dried catalyst blank with heat insulation cotton, putting the coated catalyst blank into a kiln for calcination to prepare a finished catalyst, gradually raising the calcination temperature from the normal temperature to the highest temperature of 550 ℃ within the total time of 1/2, and gradually falling back to the normal temperature within the remaining total time of 1/2 for 30 hours.
Wherein the mass ratio of the ammonia water to the calcium hydroxide is 1:1, and the pH value of the mixed liquid of the ammonia water and the calcium hydroxide is 9.
Example five:
a preparation method of a dioxin removing catalyst comprises the following steps:
1) preparation of active liquid:
active solution: heating 100L of deionized water to 60-80 ℃, stirring, adding 2.57kg of monoethanolamine, continuing to heat, adding 2.57kg of ammonium metavanadate when the temperature reaches 85-95 ℃, then preserving the heat at 95 ℃ for 30min to ensure that the ammonium metavanadate is completely dissolved, and cooling to 40-60 ℃ for heat preservation for later use.
2) Mixing operation:
the first step is as follows: weighing 85.00kg of anatase titanium dioxide, 4.0kg of silicon dioxide and a promoter precursor of 6.41kg of ammonium metatungstate, 2.52kg of cerium nitrate and 2.47kg of manganese oxalate, adding into a mixing roll, and carrying out dry mixing uniformly.
The second step is that: and sequentially adding 0.25kg of stearic acid, 0.25kg of ethylene bis fatty acid amide, 1.95kg of oxalic acid, 15L of mixed solution of ammonia water and calcium hydroxide and 80L of deionized water, and mixing to obtain a mixture I.
The third step: and adding 0.40kg of wood pulp, 5.20kg of glass fiber and all prepared active solutions into the first mixed material, and uniformly mixing to obtain a second mixed material.
The fourth step: and when the temperature of the mixture II is reduced to 55-65 ℃, adding 1.40kg of carboxymethyl cellulose and 1.40kg of ethylene oxide, and uniformly mixing to obtain a blank.
The fifth step: and sealing and preserving the blank in an environment with the temperature of 35-45 ℃ and the humidity of 45-65% for ageing for 12 hours.
And a sixth step: and filtering and forming the aged blank to obtain a honeycomb catalyst blank.
The seventh step: and drying the catalyst embryo body, wherein the drying temperature is gradually increased from 20 ℃ to 90 ℃, the humidity is decreased from 100% to 20%, and the drying time is 250 h.
The eighth step: and (3) coating the dried catalyst blank with heat insulation cotton, putting the coated catalyst blank into a kiln for calcination to prepare a finished catalyst, wherein the calcination temperature is gradually increased from the normal temperature to the maximum temperature of 630 ℃ within the total time of 1/2, and then gradually falls back to the normal temperature within the remaining total time of 1/2 for 30 hours.
Wherein the mass ratio of the ammonia water to the calcium hydroxide is 1:1, and the pH value of the mixed liquid of the ammonia water and the calcium hydroxide is 9.
Example six:
a preparation method of a dioxin removing catalyst comprises the following steps:
1) preparation of active liquid:
active solution: heating 100L of deionized water to 60-80 ℃, stirring, adding 5.14kg of monoethanolamine, continuing heating, adding 5.14kg of ammonium metavanadate when the temperature reaches 85-95 ℃, then preserving the temperature at 95 ℃ for 30min to ensure that the ammonium metavanadate is completely dissolved, cooling to 40-60 ℃ and preserving the temperature for later use.
2) Mixing operation:
the first step is as follows: 75.00kg of anatase titanium dioxide, 2.0kg of silicon dioxide and a promoter precursor of 4.28kg of ammonium metatungstate, 5.04kg of cerium nitrate and 3.29kg of manganese oxalate are weighed and added into a mixing roll for dry mixing uniformly.
The second step is that: 0.55kg of stearic acid, 0.55kg of ethylene bis fatty acid amide, 1.5kg of oxalic acid, 17L of mixed solution of ammonia water and calcium hydroxide and 65L of deionized water are sequentially added and mixed to obtain a mixture I.
The third step: and adding 0.50kg of activated carbon, 4.70kg of glass fiber and all prepared active solutions into the mixed material I, and uniformly mixing to obtain a mixed material II.
The fourth step: and when the temperature of the mixture II is reduced to 55-65 ℃, adding 2.10kg of carboxymethyl cellulose and 2.10kg of ethylene oxide, and uniformly mixing to obtain a blank.
The fifth step: and sealing and preserving the blank in an environment with the temperature of 35-45 ℃ and the humidity of 45-65% for ageing for 12 hours.
And a sixth step: and filtering and forming the aged blank to obtain a honeycomb catalyst blank.
The seventh step: and drying the catalyst embryo body, wherein the drying temperature is gradually increased from 20 ℃ to 90 ℃, the humidity is decreased from 100% to 20%, and the drying time is 350 h.
Eighth step: and (3) coating the dried catalyst blank with heat insulation cotton, putting the coated catalyst blank into a kiln for calcination to prepare a finished catalyst, gradually raising the calcination temperature from the normal temperature to the maximum temperature of 570 ℃ within the total time of 1/2, and gradually falling back to the normal temperature within the remaining total time of 1/2 for 45 hours.
Wherein the mass ratio of the ammonia water to the calcium hydroxide is 1:1, and the pH value of the mixed liquid of the ammonia water and the calcium hydroxide is 9.
The materials of the carrier and the co-catalyst components in the first to sixth examples were tested, and the results shown in the following table one were obtained:
watch 1
Performance testing
The calcined catalyst is cut into 30mm × 30mm × 300mm catalyst bodies, and the dioxin removal effect is tested on a small-sized simulated activity evaluation device.
Wherein o-dichlorobenzene is used for replacing dioxin substances, the test conditions are that the reaction temperature is 250 ℃, the space velocity is 13333h < -1 >, the oxygen concentration is 10 percent, the o-dichlorobenzene concentration is 200ppm, and the test results are shown in a second table:
watch two
| Examples | Temperature of | Efficiency of dioxin removal% |
| Example one | 250 | 90 |
| Example two | 250 | 93 |
| EXAMPLE III | 250 | 95 |
| Example four | 250 | 92 |
| EXAMPLE five | 250 | 93 |
| EXAMPLE six | 250 | 92 |
Thus, as is clear from the above table, the catalyst obtained has a high removal efficiency for o-dichlorobenzene.
In addition, the test blocks of examples one to six were subjected to the test of compressive strength using a press machine to obtain the following table three:
watch III
It can be clearly seen from the above table that the catalyst of the present application has a higher compressive strength, can be suitably used in a severer purification environment, and ensures a longer service life.
Based on the third embodiment, the contents of the precursor, the cosolvent and the silica of the co-catalyst component are respectively adjusted, and the specific adjustment result is shown in the following table four:
watch four
According to the test method of example three, the catalytic efficiency and the compressive strength of comparative examples one to nine were respectively measured, and the results are shown in table five:
watch five
As is clear from comparison of comparative examples one to four and example three, since V2O5、WO3、CeO2And MnO2The coexistence can effectively improve the efficiency of removing dioxin from the catalyst; in comparison of the fifth comparative example, the sixth comparative example and the third example, the common use of the two cosolvents also plays an important role in improving the compressive strength of the finished catalyst; furthermore, from the comparison of comparative examples seven to nine and example three, it can be seen that when the amount of the catalyst carrier is 70 to 90 parts by mass, the use of silica is controlled to be between 1 to 5 parts by mass, and it is possible to avoid waste of silica while maintaining the compressive strength of the final finished catalyst in a high state.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (7)
1. A preparation method of a dioxin removing catalyst is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
preparation of active solution:
mixing and dissolving ammonium metavanadate and monoethanolamine in deionized water at 85-95 ℃ according to the mass ratio of 1:1, and storing at constant temperature of 40-60 ℃ for later use;
mixing operation:
the method comprises the following steps: uniformly mixing titanium dioxide serving as a carrier of a catalyst, silicon dioxide, ammonium metatungstate serving as a precursor of a catalysis-assisting component, cerium nitrate and manganese oxalate with a cosolvent, an acid solution and an alkali solution to obtain a first mixture;
step two: adding the prepared active solution, the pore-forming aid and the structural aid into the mixture I, and uniformly mixing to obtain a mixture II;
step three: adding a binder into the mixture II, and uniformly mixing to finish the preparation of the blank;
step four: aging the prepared blank for 12-36 h;
step five: filtering and molding the aged blank to obtain a honeycomb catalyst blank;
step six: drying the catalyst blank, gradually increasing the drying temperature from 20 ℃ to 90 ℃, reducing the humidity from 100% to 20%, and drying for 200-400 h;
step seven: coating the dried catalyst blank with heat insulation cotton, and then putting the coated catalyst blank into a kiln for calcination to prepare a finished catalyst, wherein the calcination highest temperature is 650 ℃, and the total time is 30-50 h;
the structure auxiliary agent is glass fiber, and the cosolvent is a mixture of stearic acid and ethylene bis-fatty acid amide;
and the catalyst comprises the following components in parts by weight: 70-90 parts of TiO21.0 to 5.0 parts of SiO21.0 to 5.0 parts of V2O50.1 to 3.0 parts of MnO20.1 to 3.0 parts of CeO22.0 to 8.0 parts of WO3。
2. The method for preparing a dioxin removal catalyst according to claim 1, characterized in that: the TiO is2Is anatase titanium dioxide.
3. The method for preparing a dioxin removal catalyst according to claim 1, characterized in that: the binder is a mixture of carboxymethyl cellulose and ethylene oxide.
4. The method for preparing a dioxin removal catalyst according to claim 1, characterized in that: the pore-forming agent is one of wood pulp, activated carbon and paper pulp cotton.
5. The method for preparing a dioxin removal catalyst according to claim 1, characterized in that: the acid solution is one of lactic acid and oxalic acid.
6. The method for preparing a dioxin removal catalyst according to claim 1, characterized in that: the alkali liquor is a mixture of ammonia water and calcium hydroxide.
7. The method for preparing a dioxin removal catalyst according to claim 1, characterized in that: and the calcining temperature in the step seven is gradually increased from the normal temperature to the maximum temperature in 1/2 total time, and then gradually falls back to the normal temperature state in the rest 1/2 total time.
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| CN110252051B (en) * | 2019-05-27 | 2020-11-17 | 山东中琦环保设备制造有限公司 | Method for dedusting, desulfurizing and denitrating boiler flue gas and removing dioxin |
| CN112473657B (en) * | 2020-12-07 | 2022-02-22 | 北京建筑材料科学研究总院有限公司 | Low-vanadium catalyst for synergistically removing dioxin and mercury in flue gas and preparation method and application thereof |
| CN112973351A (en) * | 2021-02-04 | 2021-06-18 | 中国计量大学 | Ultralow emission device and method for dioxin in tail gas generated in thermal desorption process of organic contaminated soil |
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