CN114522531B - High-efficiency composite desulfurization and denitrification absorbent - Google Patents
High-efficiency composite desulfurization and denitrification absorbent Download PDFInfo
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- CN114522531B CN114522531B CN202210166401.9A CN202210166401A CN114522531B CN 114522531 B CN114522531 B CN 114522531B CN 202210166401 A CN202210166401 A CN 202210166401A CN 114522531 B CN114522531 B CN 114522531B
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Abstract
The invention relates to the technical field of desulfurization and denitrification, in particular to a high-efficiency composite desulfurization and denitrification absorbent which can improve the contact uniformity of flue gas and the absorbent, improve the desulfurization and denitrification rate, prolong the service life of the absorbent and improve the practicability; the preparation method comprises a solution preparation A, wherein the solution preparation A comprises the following raw materials in parts by weight: 28-35 parts of hypochlorite; 18-21 parts of chlorite; 0-10 parts of pH regulator; 54-62 parts of water; the solid preparation B is composed of porous particles, wherein the porous particles comprise floating particles and sinking particles, and the use ratio of the floating particles to the sinking particles is 1:3-5.
Description
Technical Field
The invention relates to the technical field of desulfurization and denitrification, in particular to a high-efficiency composite desulfurization and denitrification absorbent.
Background
The boiler is energy conversion equipment, the energy input to the boiler is chemical energy and electric energy in fuel, the boiler outputs steam, high-temperature water or organic heat carrier with certain heat energy, a large amount of flue gas can be generated after the fuel combustion is finished in the use process of the boiler, dust (comprising fly ash and carbon black) contained in the flue gas of the boiler, sulfur and nitrogen oxides are substances polluting the atmosphere, the emission index of the boiler can reach several times to tens times of environmental protection regulation index when the boiler is not purified, SO2 and NOx are main sources of atmospheric pollutants, in order to control the emission of the substances, the flue gas is the main development trend of atmospheric pollution, the desulfurization and the denitrification are carried out on the flue gas of the boiler to form an indispensable measure, the existing flue gas is subjected to pretreatment such as temperature reduction and dust removal when the flue gas is treated, the adsorption reaction is carried out in the equipment with a desulfurization and denitrification absorber, the content of the sulfur nitrogen oxides in the discharged is reduced, the pollution to the atmosphere is reduced, but the flue gas is easy to cause poor in the prior art that the desulfurization and denitrification agent is in the combustion reaction, the desulfurization and denitrification are easy to flow, the desulfurization and denitrification are easy to have poor in the prior art, the desulfurization and denitrification agent is easy to have poor in the performance and the prior art, and the desulfurization and denitrification agent is easy to flow and have poor in the performance and the performance is easy to cause the poor in the prior to flow and the desulfurization and denitrification and the denitrification.
Disclosure of Invention
In order to solve the technical problems, the invention provides the efficient composite desulfurization and denitrification absorbent which can improve the contact uniformity of the flue gas and the absorbent, improve the desulfurization and denitrification rate, prolong the service life of the absorbent and improve the practicability.
The invention discloses a high-efficiency composite desulfurization and denitrification absorbent, which comprises a solution preparation A, wherein the solution preparation A comprises the following raw materials in parts by weight:
specifically, the pH regulator is any one or a mixture of more of dilute hydrochloric acid, nitric acid and sulfuric acid.
Specifically, the absorbent further comprises a solid preparation B, wherein the solid preparation B consists of porous particles, the porous particles comprise floating particles and sinking particles, and the use ratio of the floating particles to the sinking particles is 1:3-5.
Specifically, the floating particles are prepared by carbonization and sintering of coconut shell activated carbon powder and sodium humate, and the sinking particles are prepared by carbonization and sintering of activated carbon powder, zeolite powder, borax and sodium humate.
Specifically, the floating particles comprise the following components in parts by weight:
42-50 parts of coconut shell activated carbon powder;
5-10 parts of sodium humate.
Specifically, the sinking particles comprise the following components in parts by weight:
the preparation method of the efficient composite desulfurization and denitrification absorbent comprises the following steps:
s1, preparing a solution preparation A: adding chlorite into water to be fully dissolved, adding hypochlorite into the mixed solution, and fully stirring to be dissolved;
s2, adjusting the pH value of the solution preparation A: adjusting the pH value of the solution preparation A to 5.5-6.0 by using a pH regulator, and obtaining the solution preparation A after constant volume;
s3, preparing floating particles: dissolving sodium humate in water, adding coconut shell activated carbon powder into the mixture, heating and stirring the mixture at the same time to gradually evaporate water in the mixture, kneading the mixture by a kneader, adding the mixture into a forming machine for granulating and forming, and finally sintering and carbonizing the formed granules to obtain floating granules;
s4, preparing sinking particles: dissolving sodium humate in water, adding active carbon powder, zeolite powder and borax, heating and stirring to gradually evaporate water, kneading with a kneader, granulating, and sintering and carbonizing to obtain heavy particles;
s5, split charging: and packaging the solution preparation A and the solid preparation B with equal volume amounts respectively, and proportioning the solution preparation A and the solid preparation B in a ratio of 1:1 to obtain the desulfurization and denitrification absorbent.
Specifically, the step of sintering and carbonizing the floating particles and the sinking particles comprises the following steps:
A. firstly, drying the granules at 150+/-2 ℃ to evaporate water in the granules;
B. pre-carbonizing the granule at 275+/-2 ℃ to decompose unstable components;
C. carbonizing the granules at 400+/-5 ℃;
D. finally, the granules are calcined at 500 ℃.
Specifically, the particle size of the prepared floating particles is 0.5-0.8 cm, and the particle size of the prepared floating particles is 0.3-0.5 cm.
Compared with the prior art, the invention has the beneficial effects that: when the composite desulfurization and denitrification absorbent prepared by the embodiment is used for treating boiler flue gas, firstly, the solution preparation A is led into an inhalation tower, the solid preparation B is added into the solution preparation A, the sinking particles sink into the bottom of the solution preparation A, the liquid level of the solution preparation is increased, the floating particles float on the surface of the solution preparation A and relatively play a role of a sealing cover, when the flue gas to be treated enters the adsorption tower, the flue gas passes through the solution preparation A from bottom to top, and because the solution preparation A contains a large number of porous particles, the flue gas can only pass through gaps among adjacent porous particles or pore diameters of the porous particles to circulate, so that the contact uniformity of the boiler flue gas and the solution preparation A can be effectively improved, the contact circulation time is increased by more than 50%, the desulfurization and denitrification rate can be effectively improved, the desulfurization rate is up to more than 96.0%, and the denitrification rate is up to more than 90.0%. And the service life of the absorbent can be prolonged, the product has the advantages of less formula components, easily available raw materials, simple process, convenient use and ideal effect.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
The invention relates to a high-efficiency composite desulfurization and denitrification absorbent, which comprises a solution preparation A, and the preparation method comprises the following steps: adding chlorite into water to be fully dissolved, adding hypochlorite into the mixed solution, fully stirring and dissolving, and then adjusting the pH value of the solution preparation A to 5.5 by using a pH regulator, and obtaining the solution preparation A after constant volume, wherein the addition amount of each raw material is as follows:
wherein the pH regulator is any one or a mixture of more of dilute hydrochloric acid, nitric acid and sulfuric acid.
The desulfurization and denitrification absorbent also comprises a solid preparation B, which consists of floating particles and sinking particles with the use ratio of 1:3, and the preparation method comprises the following steps:
preparing floating particles: dissolving sodium humate in water, adding coconut shell activated carbon powder into the mixture, heating and stirring the mixture at the same time to gradually evaporate water in the mixture, kneading the mixture by a kneader, adding the mixture into a forming machine for granulating and forming, and finally sintering and carbonizing the formed particles to obtain floating particles, wherein the particle size of the prepared floating particles is 0.5-0.8 cm;
preparing sinking particles: dissolving sodium humate in water, adding active carbon powder, zeolite powder and borax, heating and stirring to gradually evaporate water, kneading by a kneader, adding into a forming machine, granulating, and sintering and carbonizing the formed granules to obtain precipitated granules with the particle diameter of 0.3-0.5 cm;
the floating particles comprise the following components in parts by weight:
42 parts of coconut shell activated carbon powder;
5 parts of sodium humate.
The sinking particles comprise the following components in parts by weight:
the steps of sintering and carbonizing treatment of floating particles and sinking particles comprise:
A. firstly, drying the granules at 150+/-2 ℃ to evaporate water in the granules;
B. pre-carbonizing the granule at 275+/-2 ℃ to decompose unstable components;
C. carbonizing the granules at 400+/-5 ℃;
D. finally, the granules are calcined at 500 ℃.
And after the production of the solution preparation A and the solid preparation B is finished, packaging the solution preparation A and the solid preparation B with equal volume respectively, and obtaining the efficient composite desulfurization and denitrification absorbent according to the ratio of 1:1.
When the composite desulfurization and denitrification absorbent prepared by the embodiment is used for treating boiler flue gas, firstly, the solution preparation A is led into an inhalation tower, the solid preparation B is added into the solution preparation A, the sinking particles sink into the bottom of the solution preparation A, the liquid level of the solution preparation is increased, the floating particles float on the surface of the solution preparation A and relatively play a role of a sealing cover, when the flue gas to be treated enters the adsorption tower, the flue gas passes through the solution preparation A from bottom to top, and because the solution preparation A contains a large number of porous particles, the flue gas can only pass through gaps among adjacent porous particles or pore diameters of the porous particles to circulate, so that the contact uniformity of the boiler flue gas and the solution preparation A can be effectively improved, the contact circulation time is increased by more than 50%, the desulfurization rate of the flue gas reaches more than 96.5%, and the denitrification rate reaches more than 91.1%.
When the desulfurization and denitrification absorbent is used, when NaClO is used 2 When it is in acidic condition, it will decompose to form ClO 2 And Cl 2 The reaction formula of the gas is as follows:
ClO 2 - +H + ＝HClO 2
8HClO 2 ＝6ClO 2 +Cl 2 +4H 2 O
2ClO 2 - +Cl 2 ＝2Cl - +2ClO 2
4ClO 2 - +2H + ＝2ClO 2 - +ClO 3 - +Cl - +H 2 O
reaction with H + Increase to NaClO 2 Decomposition, clO under acidic conditions 2 The gas has a strong oxidizing property.
NaClO 2 The following reactions with NaClO will occur under acidic conditions:
2ClO 2 - +H + ＝HClO 2
ClO - +H + ＝HClO
2HClO 2 +HClO＝2ClO 2 +Cl - +H 2 O+H +
HClO is more oxidizing than HClO 2 Will oxidize it to form ClO 2 NaClO also produces Cl in a strongly acidic environment 2 And (3) gas. ClO (ClO) 2 And Cl 2 Are all strong oxidizing gases, and can directly oxidize SO 2 And NO X 。
The composite absorbent can simultaneously desulfurize and denitrate, and proves that the desulfurization rate reaches more than 96.0 percent, and the denitration rate reaches more than 90.0 percent. With NaClO 2 Or NaClO is independently used as the absorption liquid, the composite absorbent not only greatly improves the desulfurization rate and the denitration rate, but also delays the failure time of the absorbent, whichWith NaClO 2 And NaClO to generate ClO 2 Has close relation.
The denitration rate increases with an increase in the concentration of NaClO, and NaClO 2 When the molar concentration ratio of the catalyst to NaClO is (6:1), the denitration rate reaches the optimum, and the dosage is 10-20L/m 3 。
To sum up: the efficient composite desulfurization and denitrification absorbent can be widely applied to flue gas desulfurization and denitrification, and has the advantages of low cost, easily obtained materials and high efficiency.
Example 2
The invention relates to a high-efficiency composite desulfurization and denitrification absorbent, which comprises a solution preparation A, and the preparation method comprises the following steps: adding chlorite into water to be fully dissolved, adding hypochlorite into the mixed solution, fully stirring and dissolving, and then adjusting the pH value of the solution preparation A to 6.0 by using a pH regulator, and obtaining the solution preparation A after constant volume, wherein the addition amount of each raw material is as follows:
wherein the pH regulator is any one or a mixture of more of dilute hydrochloric acid, nitric acid and sulfuric acid.
The desulfurization and denitrification absorbent also comprises a solid preparation B, which consists of floating particles and sinking particles with the use ratio of 1:5, and the preparation method comprises the following steps:
preparing floating particles: dissolving sodium humate in water, adding coconut shell activated carbon powder into the mixture, heating and stirring the mixture at the same time to gradually evaporate water in the mixture, kneading the mixture by a kneader, adding the mixture into a forming machine for granulating and forming, and finally sintering and carbonizing the formed particles to obtain floating particles, wherein the particle size of the prepared floating particles is 0.5-0.8 cm;
preparing sinking particles: dissolving sodium humate in water, adding active carbon powder, zeolite powder and borax, heating and stirring to gradually evaporate water, kneading by a kneader, adding into a forming machine, granulating, and sintering and carbonizing the formed granules to obtain precipitated granules with the particle diameter of 0.3-0.5 cm;
the floating particles comprise the following components in parts by weight:
50 parts of coconut shell activated carbon powder;
10 parts of sodium humate.
The sinking particles comprise the following components in parts by weight:
the steps of sintering and carbonizing treatment of floating particles and sinking particles comprise:
A. firstly, drying the granules at 150+/-2 ℃ to evaporate water in the granules;
B. pre-carbonizing the granule at 275+/-2 ℃ to decompose unstable components;
C. carbonizing the granules at 400+/-5 ℃;
D. finally, the granules are calcined at 500 ℃.
And after the production of the solution preparation A and the solid preparation B is finished, packaging the solution preparation A and the solid preparation B with equal volume respectively, and obtaining the efficient composite desulfurization and denitrification absorbent according to the ratio of 1:1.
When the composite desulfurization and denitrification absorbent prepared by the embodiment is used for treating boiler flue gas, firstly, the solution preparation A is led into an inhalation tower, the solid preparation B is added into the solution preparation A, the sinking particles sink into the bottom of the solution preparation A, the liquid level of the solution preparation is increased, the floating particles float on the surface of the solution preparation A and relatively play a role of a sealing cover, when the flue gas to be treated enters the adsorption tower, the flue gas passes through the solution preparation A from bottom to top, and because the solution preparation A contains a large number of porous particles, the flue gas can only pass through gaps among adjacent porous particles or pore diameters of the porous particles to circulate, so that the contact uniformity of the boiler flue gas and the solution preparation A can be effectively improved, the contact circulation time is increased by more than 50%, the desulfurization rate of the flue gas reaches more than 96.7%, and the denitrification rate reaches more than 90.6%.
When the desulfurization and denitrification absorbent is used, when NaClO is used 2 When it is in acidic condition, it will decompose to form ClO 2 And Cl 2 The reaction formula of the gas is as follows:
ClO 2 - +H + ＝HClO 2
8HClO 2 ＝6ClO 2 +Cl 2 +4H 2 O
2ClO 2 - +Cl 2 ＝2Cl - +2ClO 2
4ClO 2 - +2H + ＝2ClO 2 - +ClO 3 - +Cl - +H 2 O
reaction with H + Increase to NaClO 2 Decomposition, clO under acidic conditions 2 The gas has a strong oxidizing property.
NaClO 2 The following reactions with NaClO will occur under acidic conditions:
2ClO 2 - +H + ＝HClO 2
ClO - +H + ＝HClO
2HClO 2 +HClO＝2ClO 2 +Cl - +H 2 O+H +
HClO is more oxidizing than HClO 2 Will oxidize it to form ClO 2 NaClO also produces Cl in a strongly acidic environment 2 And (3) gas. ClO (ClO) 2 And Cl 2 Are all strong oxidizing gases, and can directly oxidize SO 2 And NO X 。
The composite absorbent can simultaneously desulfurize and denitrate, and proves that the desulfurization rate reaches more than 96.0 percent, and the denitration rate reaches more than 90.0 percent. With NaClO 2 Or NaClO is independently used as absorption liquid, the composite absorbent not only greatly improves the desulfurization rate and the denitration rate, but also delaysTime to absorbent failure, which is equivalent to NaClO 2 And NaClO to generate ClO 2 Has close relation.
The denitration rate increases with an increase in the concentration of NaClO, and NaClO 2 When the molar concentration ratio of the catalyst to NaClO is (6:1), the denitration rate reaches the optimum, and the dosage is 10-20L/m 3 。
To sum up: the efficient composite desulfurization and denitrification absorbent can be widely applied to flue gas desulfurization and denitrification, and has the advantages of low cost, easily obtained materials and high efficiency.
Example 3
The invention relates to a high-efficiency composite desulfurization and denitrification absorbent, which comprises a solution preparation A, and the preparation method comprises the following steps: adding chlorite into water to be fully dissolved, adding hypochlorite into the mixed solution, fully stirring and dissolving, and then adjusting the pH value of the solution preparation A to 5.5 by using a pH regulator, and obtaining the solution preparation A after constant volume, wherein the addition amount of each raw material is as follows:
wherein the pH regulator is any one or a mixture of more of dilute hydrochloric acid, nitric acid and sulfuric acid.
The desulfurization and denitrification absorbent also comprises a solid preparation B, which consists of floating particles and sinking particles with the use ratio of 1:4, and the preparation method comprises the following steps:
preparing floating particles: dissolving sodium humate in water, adding coconut shell activated carbon powder into the mixture, heating and stirring the mixture at the same time to gradually evaporate water in the mixture, kneading the mixture by a kneader, adding the mixture into a forming machine for granulating and forming, and finally sintering and carbonizing the formed particles to obtain floating particles, wherein the particle size of the prepared floating particles is 0.5-0.8 cm;
preparing sinking particles: dissolving sodium humate in water, adding active carbon powder, zeolite powder and borax, heating and stirring to gradually evaporate water, kneading by a kneader, adding into a forming machine, granulating, and sintering and carbonizing the formed granules to obtain precipitated granules with the particle diameter of 0.3-0.5 cm;
the floating particles comprise the following components in parts by weight:
46 parts of coconut shell activated carbon powder;
8 parts of sodium humate.
The sinking particles comprise the following components in parts by weight:
the steps of sintering and carbonizing treatment of floating particles and sinking particles comprise:
A. firstly, drying the granules at 150+/-2 ℃ to evaporate water in the granules;
B. pre-carbonizing the granule at 275+/-2 ℃ to decompose unstable components;
C. carbonizing the granules at 400+/-5 ℃;
D. finally, the granules are calcined at 500 ℃.
And after the production of the solution preparation A and the solid preparation B is finished, packaging the solution preparation A and the solid preparation B with equal volume respectively, and obtaining the efficient composite desulfurization and denitrification absorbent according to the ratio of 1:1.
When the composite desulfurization and denitrification absorbent prepared by the embodiment is used for treating boiler flue gas, firstly, the solution preparation A is led into an inhalation tower, the solid preparation B is added into the solution preparation A, the sinking particles sink into the bottom of the solution preparation A, the liquid level of the solution preparation is increased, the floating particles float on the surface of the solution preparation A and relatively play a role of a sealing cover, when the flue gas to be treated enters the adsorption tower, the flue gas passes through the solution preparation A from bottom to top, and because the solution preparation A contains a large number of porous particles, the flue gas can only pass through gaps among adjacent porous particles or pore diameters of the porous particles to circulate, so that the contact uniformity of the boiler flue gas and the solution preparation A can be effectively improved, the contact circulation time is increased by more than 50%, the desulfurization rate of the flue gas reaches more than 97.2%, and the denitrification rate reaches more than 91.5%.
When the desulfurization and denitrification absorbent is used, when NaClO is used 2 When it is in acidic condition, it will decompose to form ClO 2 And Cl 2 The reaction formula of the gas is as follows:
ClO 2 - +H + ＝HClO 2
8HClO 2 ＝6ClO 2 +Cl 2 +4H 2 O
2ClO 2 - +Cl 2 ＝2Cl - +2ClO 2
4ClO 2 - +2H + ＝2ClO 2 - +ClO 3 - +Cl - +H 2 O
reaction with H + Increase to NaClO 2 Decomposition, clO under acidic conditions 2 The gas has a strong oxidizing property.
NaClO 2 The following reactions with NaClO will occur under acidic conditions:
2ClO 2 - +H + ＝HClO 2
ClO - +H + ＝HClO
2HClO 2 +HClO＝2ClO 2 +Cl - +H 2 O+H +
HClO is more oxidizing than HClO 2 Will oxidize it to form ClO 2 NaClO also produces Cl in a strongly acidic environment 2 And (3) gas. ClO (ClO) 2 And Cl 2 Are all strong oxidizing gases, and can directly oxidize SO 2 And NO X 。
The composite absorbent can simultaneously desulfurize and denitrate, and proves that the desulfurization rate reaches more than 96.0 percent, and the denitration rate reaches more than 90.0 percent. With NaClO 2 Or compared with NaClO alone as the absorption liquid, the composite absorbent not only greatly improves the desulfurization rate and the denitration rate, but also delays the failure time of the absorbent, which is compared with NaClO 2 And NaClO to generate ClO 2 Has close relation.
And denitration rateAs the concentration of NaClO increases, the concentration of NaClO increases 2 When the molar concentration ratio of the catalyst to NaClO is (6:1), the denitration rate reaches the optimum, and the dosage is 10-20L/m 3 。
To sum up: the efficient composite desulfurization and denitrification absorbent can be widely applied to flue gas desulfurization and denitrification, and has the advantages of low cost, easily obtained materials and high efficiency.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (4)
1. The efficient composite desulfurization and denitrification absorbent is characterized by comprising a solution preparation A, wherein the solution preparation A comprises the following raw materials in parts by weight:
28-35 parts of hypochlorite;
18-21 parts of chlorite;
0-10 parts of pH regulator;
54-62 parts of water;
the solid preparation B consists of porous particles, wherein the porous particles comprise floating particles and sinking particles, and the use ratio of the floating particles to the sinking particles is 1:3-5;
the floating particles are prepared by carbonization and sintering of coconut shell activated carbon powder and sodium humate, and the sinking particles are prepared by carbonization and sintering of activated carbon powder, zeolite powder, borax and sodium humate;
the floating particles comprise the following components in parts by weight:
42-50 parts of coconut shell activated carbon powder;
5-10 parts of sodium humate;
the sinking particles comprise the following components in parts by weight:
30-45 parts of activated carbon powder;
42-57 parts of zeolite powder;
17-25 parts of borax;
12-18 parts of sodium humate;
the preparation method comprises the following steps:
s1, preparing a solution preparation A: adding chlorite into water to be fully dissolved, adding hypochlorite into the mixed solution, and fully stirring to be dissolved;
s2, adjusting the pH value of the solution preparation A: adjusting the pH value of the solution preparation A to 5.5-6.0 by using a pH regulator, and obtaining the solution preparation A after constant volume;
s3, preparing floating particles: dissolving sodium humate in water, adding coconut shell activated carbon powder into the mixture, heating and stirring the mixture at the same time to gradually evaporate water in the mixture, kneading the mixture by a kneader, adding the mixture into a forming machine for granulating and forming, and finally sintering and carbonizing the formed granules to obtain floating granules;
s4, preparing sinking particles: dissolving sodium humate in water, adding active carbon powder, zeolite powder and borax, heating and stirring to gradually evaporate water, kneading with a kneader, granulating, and sintering and carbonizing to obtain heavy particles;
s5, split charging: and packaging the solution preparation A and the solid preparation B with equal volume amounts respectively, and proportioning the solution preparation A and the solid preparation B in a ratio of 1:1 to obtain the desulfurization and denitrification absorbent.
2. The efficient composite desulfurization and denitrification absorbent according to claim 1, wherein the pH adjuster is a mixture of any one or more of dilute hydrochloric acid, nitric acid and sulfuric acid.
3. The efficient composite desulfurization and denitrification absorbent according to claim 2, wherein the step of sintering and carbonizing floating particles and sinking particles comprises:
A. firstly, drying the granules at 150+/-2 ℃ to evaporate water in the granules;
B. pre-carbonizing the granule at 275+/-2 ℃ to decompose unstable components;
C. carbonizing the granules at 400+/-5 ℃;
D. finally, the granules are calcined at 500 ℃.
4. The efficient composite desulfurization and denitrification absorbent according to claim 3, wherein the prepared floating particles have a particle size of 0.5-0.8 cm, and the precipitated particles have a particle size of 0.3-0.5 cm.
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