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CN113877638B - Preparation method for preparing denitration and dioxin removal VOCs integrated catalyst by fractional precipitation method and prepared catalyst - Google Patents

Preparation method for preparing denitration and dioxin removal VOCs integrated catalyst by fractional precipitation method and prepared catalyst Download PDF

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CN113877638B
CN113877638B CN202111049719.0A CN202111049719A CN113877638B CN 113877638 B CN113877638 B CN 113877638B CN 202111049719 A CN202111049719 A CN 202111049719A CN 113877638 B CN113877638 B CN 113877638B
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denitration
steps
dioxin
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CN113877638A (en
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王光应
赵羽
梁燕
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Anhui Yuanchen Environmental Protection Science and Technology Co Ltd
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Abstract

The invention discloses a preparation method of a denitration and dioxin removal VOCs integrated catalyst by a fractional precipitation method, and relates to the technical field of catalysts. The invention also provides the catalyst prepared by the method. The invention has the beneficial effects that: the catalyst can react with NO at 200 DEG C x The removal efficiency of dioxin and VOCs respectively reaches 80%, 90% and more than 90%.

Description

Preparation method for preparing denitration and dioxin removal VOCs integrated catalyst by fractional precipitation method and prepared catalyst
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method for preparing a denitration and dioxin removal and VOCs removal integrated catalyst by a fractional precipitation method and the prepared catalyst.
Background
The earliest multi-pollutant emission reduction technology applied to industrial production is an activated carbon method which can effectively remove SO in sintering flue gas 2 、NO x The activated carbon can be resolved and regenerated, but the method has huge investment and high operation cost. Catalysts currently on the market are generally directed only to dioxins or NO x Or the removal of single substances of VOCs, or the removal of two substances, such as a denitration and dioxin removal catalyst disclosed in patent publication No. CN 106345454A. The stepwise catalytic removal requires more complex engineering equipment, resulting in increased costs.
Disclosure of Invention
The technical problem to be solved by the invention is that NO is removed by step-by-step catalysis in the prior art x More complex engineering equipment is needed for dioxin and VOCs, so that the cost is increased, and an integrated catalyst for preparing denitration and denitrification and VOCs by a step-by-step precipitation method is providedA preparation method of the catalyst and the catalyst prepared by the method.
The invention solves the technical problems by the following technical means:
the preparation method of the integrated catalyst for denitration and dioxin removal and VOCs (volatile organic compounds) by a fractional precipitation method comprises the following steps:
(1) Mixing and stirring nano titanium dioxide and water to obtain a carrier suspension;
(2) Slowly adding cobalt precursor salt solution into the carrier suspension in the step (1), simultaneously dripping alkali liquor to adjust the pH value, standing the obtained mixed suspension, carrying out suction filtration and separation, and drying the obtained solid and roasting at low temperature to obtain an intermediate A;
(3) Mixing and stirring a manganese precursor salt solution and the intermediate A, slowly adding alkali liquor to adjust the pH value, standing the obtained mixed suspension, carrying out suction filtration and separation, and drying and roasting the obtained solid at a low temperature to obtain an intermediate B;
(4) Stirring and mixing a copper precursor salt solution and an intermediate B, slowly adding alkali liquor to adjust the pH value, standing the obtained mixed suspension, carrying out suction filtration and separation, and drying and roasting the obtained solid at a high temperature to obtain the denitration and dioxin and VOCs removal integrated catalyst.
The beneficial effects are that: the catalyst prepared by the step-by-step method is prepared at the reaction temperature of 200 o C, reach NO x The removal rate is more than 80%, the dioxin removal rate is more than 90%, and the VOCs removal efficiency is more than 90%.
If the step precipitation method is not adopted, the obtained catalyst pair NO x The removal efficiency of dioxin and VOCs is low.
The cobalt oxide and the manganese oxide can provide active sites for SCR denitration reaction, and NO x Conversion to N 2 And H 2 O; copper oxide and manganese oxide provide active sites for the catalytic oxidative degradation of dioxins and VOCs, and thoroughly mineralize the dioxins and the VOCs into CO 2 、H 2 O and HCl. Therefore, the ternary composite oxide catalyst in the invention can cooperatively remove NO x Dioxin and VOCs, is a three-way catalyst, can simplify the post-treatment equipment of the flue gas,and reduces the dosage and cost of the catalyst.
The addition of the cobalt oxide can effectively reduce the NO adsorbed on the surface of the catalyst x Activation energy and increase NO in gas phase 2 Thereby significantly increasing the SCR denitration activity of the catalyst.
Manganese oxide mainly improves the low-temperature SCR activity of the catalyst when the smoke temperature is higher than 300 DEG C o And C, when hydrocarbon and HCl exist in the flue gas, the concentration of dioxin substances at the SCR outlet is larger than that at the SCR inlet. So that the optimal temperature for the catalytic oxidation of the dioxin is 300 ℃ in order to prevent the regeneration of the dioxin and ensure the removal efficiency of the dioxin o And C or less.
The catalytic degradation of dioxin can be divided into three steps: the dioxin is adsorbed on the surface active site of the catalyst, the dioxin obtains lattice oxygen of the surface active site of the catalyst, and the dioxin obtaining the lattice oxygen is decomposed until the dioxin is completely mineralized. The copper oxide can provide a large amount of lattice oxygen for the catalytic degradation process of the dioxin, so the catalyst modified by the copper oxide has higher dioxin removal performance. The VOCs degradation process is similar to dioxins.
Preferably, the specific surface area of the nano titanium dioxide is 50-150m 2 /g。
The beneficial effects are that: the nano titanium dioxide carrier has high specific surface area, can effectively disperse active components, and has SCR denitration activity.
Preferably, the specific surface area of the nano titanium dioxide is 100m 2 /g。
Preferably, the mass ratio of the metal oxide in the integrated catalyst for denitration and dioxin removal and VOCs is cobalt oxide: manganese oxide: copper oxide = 0.5-1.5:5-15:1-3.
Preferably, the cobalt, manganese, copper precursor salts include nitrates, chlorates.
Preferably, the lye in the steps (2), (3) and (4) is NaOH, KOH, na 2 CO 3 、K 2 CO 3 、NaHCO 3 And KHCO 3 The concentration of the alkali liquor is 1-10M.
Preferably, in the steps (2), (3) and (4), alkali liquor is adopted to adjust the pH value of the mixed suspension to 9-11, and the standing time of the mixed suspension is 2-12h.
Preferably, the drying temperature in the steps (2), (3) and (4) is 80-100 ℃.
Preferably, the firing temperature in the steps (2) and (3) is 150 o C。
Preferably, the calcination temperature in the step (4) is 300-450 DEG C o And C, the roasting atmosphere is air.
The integrated catalyst for denitration and dioxin removal and VOCs removal prepared by the method is provided.
The invention has the advantages that: the catalyst prepared by the step-by-step method is prepared at the reaction temperature of 200 o C, reach NO x The removal rate is more than 80%, the dioxin removal rate is more than 90%, and the VOCs removal efficiency is more than 90%.
If the step precipitation method is not adopted, the obtained catalyst pair NO x The removal efficiency of dioxin and VOCs is low.
The cobalt oxide and the manganese oxide can provide active sites for SCR denitration reaction, and NO x Conversion to N 2 And H 2 O; copper oxide and manganese oxide provide active sites for the catalytic oxidative degradation of dioxins and VOCs, and thoroughly mineralize the dioxins and the VOCs into CO 2 、H 2 O and HCl. Therefore, the ternary composite oxide catalyst in the invention can cooperatively remove NO x Dioxin and VOCs are three-way catalysts, so that the flue gas aftertreatment equipment can be simplified, and the consumption and cost of the catalysts can be reduced.
The addition of the cobalt oxide can effectively reduce the NO adsorbed on the surface of the catalyst x Activation energy and increase NO in gas phase 2 Thereby significantly increasing the SCR denitration activity of the catalyst.
Manganese oxide mainly improves the low-temperature SCR activity of the catalyst when the smoke temperature is higher than 300 DEG C o And C, when hydrocarbon and HCl exist in the flue gas, the concentration of dioxin substances at the SCR outlet is larger than that at the SCR inlet. So in order to preventRegeneration of dioxin, ensuring removal efficiency of dioxin, and optimal temperature of catalytic oxidation of dioxin is 300 o And C or less.
The catalytic degradation of dioxin can be divided into three steps: the dioxin is adsorbed on the surface active site of the catalyst, the dioxin obtains lattice oxygen of the surface active site of the catalyst, and the dioxin obtaining the lattice oxygen is decomposed until the dioxin is completely mineralized. The copper oxide can provide a large amount of lattice oxygen for the catalytic degradation process of the dioxin, so the catalyst modified by the copper oxide has higher dioxin removal performance. The VOCs degradation process is similar to dioxins.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
The preparation method of the integrated catalyst for denitration and dioxin removal and VOCs (volatile organic compounds) by a fractional precipitation method comprises the following steps:
1) 10g of nano titanium dioxide (specific surface area 50m 2 Mixing with 200mL water to obtain carrier suspension, and stirring continuously;
2) 0.446g Co (NO) 3 ) 2 ·6H 2 O is dissolved in 200mL of water to obtain a mixed metal salt solution with a certain concentration, and the mixed metal salt solution is slowly added into the carrier suspension, and NaOH with the total concentration of 1M is dripped simultaneously: na (Na) 2 CO 3 =1: 1 (molar ratio) alkali liquor to adjust pH value9, standing the obtained mixed suspension for 2h to fully precipitate metal salt, filtering and separating to obtain solid 80 o C, drying and roasting at 150 ℃ for 3 hours to obtain an intermediate A;
3) 5.80g Mn (NO) 3 ) 2 (50% aqueous solution) and the intermediate A are stirred and mixed in 200mL of water to obtain a mixed metal salt solution with a certain concentration, and NaOH with a total concentration of 1M is slowly dripped: na (Na) 2 CO 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to 9, the obtained mixed suspension is kept stand for 2 hours to enable metal salts to be fully precipitated, suction filtration and separation are carried out, and the obtained solid is dried at 80 ℃ and then baked at 150 ℃ for 3 hours to obtain an intermediate B;
4) 0.698g Cu (NO) 3 ) 2 ·3H 2 And (3) stirring and mixing O and the intermediate B in 200mL of water to obtain a mixed metal salt solution with a certain concentration, slowly adding alkali liquor to adjust the pH value to 9, standing the obtained mixed suspension for 2 hours to enable metal salt to be fully precipitated, carrying out suction filtration and separation, and drying the obtained solid at 80 ℃ and then roasting at 300 ℃ for 3 hours to obtain the integrated catalyst for denitration and dioxin removal and VOCs.
Example 2
The preparation method of the integrated catalyst for denitration and dioxin removal and VOCs (volatile organic compounds) by a fractional precipitation method comprises the following steps:
1) 10g of nano titanium dioxide (specific surface area 100m 2 Mixing with 200mL water to obtain carrier suspension, and stirring continuously;
2) 0.892g Co (NO 3 ) 2 ·6H 2 O is dissolved in 200mL of water to obtain a mixed metal salt solution with a certain concentration, and the mixed metal salt solution is slowly added into the carrier suspension, and KOH with a total concentration of 5M is added dropwise at the same time: k (K) 2 CO 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to 10, the obtained mixed suspension is stood for 7 hours to enable metal salt to be fully precipitated, suction filtration is carried out for separation, and the obtained solid is 90 percent o C, drying and roasting at 150 ℃ for 3 hours to obtain an intermediate A;
3) 11.6g Mn (NO) 3 ) 2 (50% aqueous solution) and intermediate A are stirred and mixed in 200mL of water to obtain mixed gold with a certain concentrationSlowly dropping KOH with the total concentration of 5M into a salt solution: k (K) 2 CO 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to be 10, the obtained mixed suspension is kept stand for 7 hours to enable metal salts to be fully precipitated, suction filtration and separation are carried out, and the obtained solid is dried at 90 ℃ and then burned for 3 hours at 150 ℃ to obtain an intermediate B;
4) 1.396g Cu (NO) 3 ) 2 ·3H 2 And (3) stirring and mixing O and the intermediate B in 200mL of water to obtain a mixed metal salt solution with a certain concentration, slowly adding alkali liquor to adjust the pH value to 10, standing the obtained mixed suspension for 7h to enable metal salt to be fully precipitated, carrying out suction filtration and separation, drying the obtained solid at 90 ℃, and then roasting at 400 ℃ for 3 hours to obtain the integrated catalyst for denitration and dioxin and VOCs removal.
Example 3
The preparation method of the integrated catalyst for denitration and dioxin removal and VOCs (volatile organic compounds) by a fractional precipitation method comprises the following steps:
1) 10g of nano titanium dioxide (specific surface area 150m 2 Mixing with 200mL water to obtain carrier suspension, and stirring continuously;
2) 1.0938g CoCl 2 ·6H 2 O is dissolved in 200mL of water to obtain a mixed metal salt solution with a certain concentration, and the mixed metal salt solution is slowly added into the carrier suspension, and NaOH with the total concentration of 10M is dripped simultaneously: naHCO (NaHCO) 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to 11, the obtained mixed suspension is stood for 12 hours to fully precipitate metal salt, the suction filtration is carried out, and the obtained solid is 100 o C, drying and roasting at 150 ℃ for 3 hours to obtain an intermediate A;
3) 6.11g MnCl 2 And the intermediate A are stirred and mixed in 200mL of water to obtain a mixed metal salt solution with a certain concentration, and NaOH with the total concentration of 10M is slowly dripped in: naHCO (NaHCO) 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to be 11, the obtained mixed suspension is kept stand for 12 hours to enable metal salts to be fully precipitated, suction filtration and separation are carried out, and the obtained solid is dried at 100 ℃ and then baked at 150 ℃ for 3 hours to obtain an intermediate B;
4) 1.478g of CuCl 2 ·2H 2 O and intermediate B are stirred and mixed in 200mL of waterMixing to obtain a mixed metal salt solution with a certain concentration, slowly adding alkali liquor to adjust the pH value to 11, standing the obtained mixed suspension for 12 hours to fully precipitate the metal salt, carrying out suction filtration and separation, drying the obtained solid at 100 ℃, and then carrying out high-temperature roasting at 450 ℃ for 3 hours to obtain the integrated catalyst for denitration and denitrification and dioxin and VOCs removal.
Comparative example 1
1) 10g of nano titanium dioxide (specific surface area 50m 2 Mixing with 200mL water to obtain carrier suspension, and stirring continuously;
2) 5.80g Mn (NO) 3 ) 2 (50% aqueous solution) and 200mL of water to obtain a mixed metal salt solution of a certain concentration, slowly adding the mixed metal salt solution into the carrier suspension, and simultaneously dropwise adding NaOH of which the total concentration is 1M: na (Na) 2 CO 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to 9, the obtained mixed suspension is kept stand for 2 hours to fully precipitate metal salts, suction filtration is carried out for separation, and the obtained solid is dried at 80 ℃ and then baked at 300 ℃ for 3 hours.
Comparative example 2
1) 10g of nano titanium dioxide (specific surface area 50m 2 Mixing with 200mL water to obtain carrier suspension, and stirring continuously;
2) 0.446g Co (NO) 3 ) 2 ·6H 2 O is dissolved in 200mL of water to obtain a mixed metal salt solution with a certain concentration, and the mixed metal salt solution is slowly added into the carrier suspension, and NaOH with the total concentration of 1M is dripped simultaneously: na (Na) 2 CO 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to 9, the obtained mixed suspension is stood for 2 hours to fully precipitate metal salt, suction filtration is carried out for separation, and the obtained solid is 80 o C, drying and roasting at 150 ℃ for 3 hours to obtain an intermediate A;
3) 0.698g Cu (NO) 3 ) 2 ·3H 2 O and the intermediate A are stirred and mixed in 200mL of water to obtain a mixed metal salt solution with a certain concentration, and NaOH with the total concentration of 1M is slowly dripped in: na (Na) 2 CO 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to 9, the obtained mixed suspension is stood for 2 hours to fully precipitate metal salt, suction filtration is carried out for separation, and the obtained solid is dried at 80 DEG CRoasting at 300 deg.c for 3 hr.
Comparative example 3
1) 10g of nano titanium dioxide (specific surface area 50m 2 Mixing with 200mL water to obtain carrier suspension, and stirring continuously;
2) 0.446g Co (NO) 3 ) 2 ·6H 2 O、5.80g Mn(NO 3 ) 2 (50% aqueous solution) and 0.698g Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 200mL of water to obtain a mixed metal salt solution with a certain concentration, and the mixed metal salt solution is slowly added into the carrier suspension, and NaOH with the total concentration of 1M is dripped simultaneously: na (Na) 2 CO 3 =1: 1 (molar ratio) alkali liquor is used for regulating the pH value to 9, the obtained mixed suspension is kept stand for 2 hours to fully precipitate metal salts, suction filtration is carried out for separation, and the obtained solid is dried at 80 ℃ and then baked at 300 ℃ for 3 hours.
Experimental data and analysis:
the performance of the catalysts obtained in example 1, comparative example 1 to comparative example 3 was measured.
Wherein NO is x The method for measuring the removal rate of dioxin and VOCs is as follows:
performance testing was performed in a fixed bed, with the catalyst cut into 20mm x 30mm size samples along the tunnel direction and placed into the bed along the reactor axis. The smoke component is NO (1000 ppm) and NH 3 (1000 ppm), chlorobenzene (2 ppm), toluene (200 ppm), O 2 (6vol.%)、N 2 Is used as carrier gas, and the airspeed of the mixed gas is 6000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature was 200 ℃. Before the reaction gas is introduced, air is introduced into the fixed bed reactor, the temperature is raised to 400 ℃ and kept for 4 hours, and the reaction gas is introduced after the reaction temperature is reduced to carry out performance test.
The catalyst of the present invention was found to be capable of reacting at a temperature of 200 o C, reach NO x The removal rate is more than 80%, the dioxin removal rate is more than 90%, and the VOCs removal efficiency is more than 90%. The catalyst has good service performance and can be used for treating NO in flue gas x And the dioxin and VOCs are effectively removed.
In comparative example 1, only a catalyst of manganese salt was added,can reach NO x The removal rate is more than 80 percent, but the removal activity to dioxin and VOCs is not realized; in comparative example 2, only copper salt and cobalt salt are added, the removal rate of dioxin and VOCs is over 90 percent, but NO NO is contained x And (5) removing the function. So that the NO can be realized only by compounding three metals of manganese, cobalt and copper x Three-effect synergistic removal of dioxin and VOCs. The catalyst obtained by coprecipitation of three metal salts in comparative example 3, although it had NO x Three-effect synergistic removal catalytic activity of dioxin and VOCs, but lower activity, NO at 200 DEG C x The removal efficiencies of dioxin and VOCs are respectively 50%, 30% and 35%. Therefore, the step-by-step precipitation method can form a good catalytic interface between the metal oxides, and has higher catalytic removal activity compared with a metal oxide solid solution formed by coprecipitation.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The preparation method of the integrated catalyst for denitration and dioxin removal and VOCs (volatile organic compounds) by a fractional precipitation method is characterized by comprising the following steps of: the method comprises the following steps:
(1) Mixing and stirring nano titanium dioxide and water to obtain a carrier suspension;
(2) Slowly adding cobalt precursor salt solution into the carrier suspension in the step (1), simultaneously dripping alkali liquor to adjust the pH value, standing the obtained mixed suspension, carrying out suction filtration and separation, and drying the obtained solid and roasting at low temperature to obtain an intermediate A;
(3) Mixing and stirring a manganese precursor salt solution and the intermediate A, slowly adding alkali liquor to adjust the pH value, standing the obtained mixed suspension, carrying out suction filtration and separation, and drying and roasting the obtained solid at a low temperature to obtain an intermediate B;
(4) Stirring and mixing a copper precursor salt solution and an intermediate B, slowly adding alkali liquor to adjust the pH value, standing the obtained mixed suspension, carrying out suction filtration and separation, and drying and roasting the obtained solid at a high temperature to obtain the denitration and dioxin and VOCs removal integrated catalyst.
2. The method for preparing the integrated catalyst for denitration and denitrification and dioxin removal and VOCs by using the fractional precipitation method according to claim 1, which is characterized by comprising the following steps: the specific surface area of the nano titanium dioxide is 50-150m 2 /g。
3. The method for preparing the integrated catalyst for denitration and denitrification and dioxin removal and VOCs by using the fractional precipitation method according to claim 1, which is characterized by comprising the following steps: the mass ratio of the metal oxides in the denitration and dioxin removal VOCs integrated catalyst is cobalt oxide: manganese oxide: copper oxide = 0.5-1.5:5-15:1-3.
4. The method for preparing the integrated catalyst for denitration and denitrification and dioxin removal and VOCs by using the fractional precipitation method according to claim 1, which is characterized by comprising the following steps: the cobalt, manganese and copper precursor salts comprise nitrate and chlorate.
5. The method for preparing the integrated catalyst for denitration and denitrification and dioxin removal and VOCs by using the fractional precipitation method according to claim 1, which is characterized by comprising the following steps: the alkali liquor in the steps (2), (3) and (4) is NaOH, KOH, na 2 CO 3 、K 2 CO 3 、NaHCO 3 And KHCO 3 The concentration of the alkali liquor is 1-10M.
6. The method for preparing the integrated catalyst for denitration and denitrification and dioxin removal and VOCs by using the fractional precipitation method according to claim 1, which is characterized by comprising the following steps: and (3) in the steps (2), (3) and (4), the pH value of the mixed suspension is regulated to 9-11 by adopting alkali liquor, and the standing time of the mixed suspension is 2-12h.
7. The method for preparing the integrated catalyst for denitration and denitrification and dioxin removal and VOCs by using the fractional precipitation method according to claim 1, which is characterized by comprising the following steps: the drying temperature in the steps (2), (3) and (4) is 80-100 ℃.
8. The method for preparing the integrated catalyst for denitration and denitrification and dioxin removal and VOCs by using the fractional precipitation method according to claim 1, which is characterized by comprising the following steps: the roasting temperature in the steps (2) and (3) is 150 o C。
9. The method for preparing the integrated catalyst for denitration and denitrification and dioxin removal and VOCs by using the fractional precipitation method according to claim 1, which is characterized by comprising the following steps: the roasting temperature in the step (4) is 300-450 DEG C o And C, the roasting atmosphere is air.
10. A denitration and dioxin removal VOCs integrated catalyst produced by the production method of any one of claims 1 to 9.
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