CN113117512A - Wet flue gas desulfurization solid synergist and preparation method thereof - Google Patents

Wet flue gas desulfurization solid synergist and preparation method thereof Download PDF

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CN113117512A
CN113117512A CN202110448572.6A CN202110448572A CN113117512A CN 113117512 A CN113117512 A CN 113117512A CN 202110448572 A CN202110448572 A CN 202110448572A CN 113117512 A CN113117512 A CN 113117512A
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flue gas
gas desulfurization
wet flue
synergist
solid synergist
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刘大华
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Quanzhou Boyin Information Technology Co ltd
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    • 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
    • B01D53/81—Solid phase processes
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

The invention provides a solid synergist for wet flue gas desulfurization and a preparation method thereof, wherein the solid synergist comprises the following components in percentage by weight: 60% -80% of buffering agent, 10% -25% of surfactant, 10% -20% of inorganic salt and 2% -8% of adhesive. The preparation method of the solid synergist for wet flue gas desulfurization comprises the steps of dissolving a buffering agent and a binder in water, and uniformly stirring to obtain a binder solution for later use; adding a surfactant and inorganic salt into a fluidized bed for preheating, spraying the adhesive solution when the temperature of the surfactant and the inorganic salt reaches 35-50 ℃, and drying after spraying to obtain dry particles; and (4) finishing the dry particles. The use method of the wet flue gas desulfurization solid synergist comprises the step of adding the wet flue gas desulfurization solid synergist with the concentration of 20-50 mg/L into a calcium absorbent. The synergist provided by the invention has the advantages of quick effect, low consumption, simple formula, high desulfurization efficiency, simple preparation method and good process reproducibility, and the components in the produced product are uniformly distributed.

Description

Wet flue gas desulfurization solid synergist and preparation method thereof
Technical Field
The invention relates to the technical field of flue gas desulfurization, in particular to a solid synergist for wet flue gas desulfurization and a preparation method thereof.
Background
Sulfur dioxide has great harm to the environment, can cause acid rain and acid mist, has a corrosive effect on the environment, and also has a carcinogenic effect on human bodies. In recent years, the haze in coastal industrial areas is seriously damaged, and one of main components of the haze is sulfur dioxide.
With the increasing of the force of sulfur dioxide emission reduction policy in China and the popularization and application of various desulfurization technologies in coal-fired power plants, the sulfur dioxide emission is effectively controlled. However, in the actual operation process of the power plant, various unstable factors such as large coal quality fluctuation, uneven coal types, variation of power generation load of the boiler, unstable quality of the calcium absorbent and the like are faced, and a great interference effect is achieved on the operation of the desulfurizing tower.
After the issuance of new environmental regulations, many power plants are difficult to reach the maximum standard and cannot well meet the emission control of sulfur dioxide, so that the power plants are required to upgrade and modify the existing desulfurization system aiming at a new emission limit value, which means expensive modification cost and huge loss of shutdown. Therefore, the method improves the desulfurization efficiency on the basis of the traditional desulfurization system, and becomes the first choice of enterprises. The desulfurization additive is the preferred scheme under the condition, and compared with a modified device, the desulfurization additive has the advantages of low cost and wide applicability.
At present, additives for limestone wet desulphurization are mainly classified into three types: inorganic additives with high efficiency but large dosage, organic additives with slow effect but small dosage, and composite additives with the advantages of the two.
For example, the Chinese patent application publication No. CN 105289269A of 'a desulfurization synergist for a wet flue gas desulfurization system of a thermal power plant' discloses a desulfurization synergist for a wet flue gas desulfurization system of a thermal power plant, which comprises the following components: the composite material comprises a surfactant, a cosolvent, a PH buffer and an oxidation catalyst, wherein the preferable mass percentage is as follows: 40-60% of surfactant, 20-40% of cosolvent, 5-15% of PH buffer and 2-5% of oxidation catalyst. The desulfurization synergist is added into a calcium absorbent, and the use concentration is 150 mg/L-600 mg/L. The desulfurization synergist can promote the dissolution balance of the calcium absorbent to move to the positive direction and improve the solubility of calcium; the pH value of a gas-liquid interface is stabilized, and the dissolving speed of sulfur dioxide is increased; the oxidation speed is improved, and the generation of gypsum is accelerated; the circulation amount of the absorption slurry is reduced, the consumption of the absorption slurry is reduced, and the effects of saving energy, reducing consumption, lowering cost and improving efficiency are achieved. However, the novel compound desulfurization synergist has a complex formula and needs to be used in a high dosage.
Also for example, the Chinese patent application publication No. CN 104722205A of "a limestone-gypsum wet flue gas desulfurization synergist" discloses a limestone-gypsum wet flue gas desulfurization synergist, which consists of the following components: sebacic acid, ferric oxide and sodium hexametaphosphate. Wherein the content of the sebacic acid is 80-90%. Wherein the content of ferric oxide is 5-15%. Wherein the content of sodium hexametaphosphate is 3-8%. The optimal use concentration is 1.2-1.5 g/L. The desulfurization synergist of the invention is beneficial to improving the dissolution rate of limestone and the absorption rate of SO 2; meanwhile, the metal oxide with catalytic oxidation can improve the oxidation rate of the calcium sulfite; the dispersing agent can ensure the dispersibility of solid particles in the slurry and reduce the equipment blockage caused by the precipitation of the solid particles. The synergist of the invention can improve the wet desulphurization efficiency by 5-10%, reduce the consumption of limestone and improve the reliability of equipment operation. However, analysis shows that the amount of the synergist in the invention is extremely high, and a new pollutant, namely phosphorus, is introduced.
Disclosure of Invention
The invention provides a solid synergist for wet flue gas desulfurization and a preparation method thereof for solving the technical problems, wherein a buffer agent and an adhesive are dissolved in water to prepare an adhesive solution; adding a surfactant and inorganic salt into a fluidized bed for preheating, spraying the adhesive solution after the preset material temperature is reached, and drying after spraying to obtain dry particles; and finally, the obtained dry particles are granulated, so that the effects of simple preparation method, good process reproducibility and uniform distribution of all components in the produced product are achieved.
The invention relates to a solid synergist for wet flue gas desulfurization and a preparation method thereof, and the technical scheme is as follows:
a solid synergist for wet flue gas desulfurization comprises the following components in percentage by weight: 60% -80% of buffering agent, 10% -25% of surfactant, 10% -20% of inorganic salt and 2% -8% of adhesive.
Preferably in any one of the above embodiments, the buffer comprises one or more of citric acid, sodium citrate, succinic acid, adipic acid, tartaric acid, ascorbic acid, benzoic acid, malic acid.
In any of the above embodiments, preferably, the surfactant comprises one or more of stearic acid, sodium dodecylbenzenesulfonate, and sodium dioctyl sulfosuccinate.
In any of the above schemes, preferably, the inorganic salt is one or more of sodium chloride, potassium carbonate, potassium oxalate, magnesium sulfate, and calcium sulfate.
In any of the above embodiments, preferably, the binder is one or more of pregelatinized gelatin, povidone, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, powdered sugar, starch slurry, and gelatin.
In any of the above aspects, preferably, the binder is povidone.
Preferably in any of the above embodiments, the binder is povidone K29/32.
In any of the above schemes, it is preferable that the D90 of the wet flue gas desulfurization solid synergist is less than or equal to 100 μm. Said "D90"means the particle size corresponding to 90% of the cumulative particle size distribution of a sample. Its physical meaning is that 90% of the particles have a particle size smaller than that of the particles, e.g. "D90Not more than 100 μm "means" 90% of particles not more than 100. mu.m ".
A preparation method of a wet flue gas desulfurization solid synergist comprises the following steps:
dissolving a buffering agent and an adhesive in water, and uniformly stirring to obtain an adhesive solution for later use;
adding a surfactant and an inorganic salt into a fluidized bed for preheating, and spraying the adhesive solution when the temperature of the surfactant and the inorganic salt reaches 35-50 ℃;
after the spraying is finished, drying to obtain dry particles;
and (4) finishing the dry particles.
In any of the above embodiments, it is preferable that the binder solution is sprayed at an atomization pressure of 0.5bar to 2.0bar and a spray velocity of 3.0g/min to 20.0 g/min.
The invention has the beneficial effects that:
1. the solid synergist for wet flue gas desulfurization provided by the invention has the advantages of small particle size, more gaps and large specific surface area, and can greatly improve the desulfurization efficiency, so that the dosage of the synergist is less.
2. The solid synergist for wet flue gas desulfurization provided by the invention has the advantages of quick effect, low consumption, simple formula, overall reduced cost and certain economic benefit.
3. The preparation method of the wet flue gas desulfurization solid synergist provided by the invention adopts a wet granulation technology to prepare the synergist, the method is simple, the process reproducibility is good, and the components in the produced product are uniformly distributed.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the following further discloses some non-limiting examples to further explain the present invention in detail.
In the examples described below, all temperatures are given in degrees Celsius unless otherwise indicated. The reagents used are either commercially available or can be prepared by the methods described herein.
Example 1
A solid synergist for wet flue gas desulfurization is prepared from the following raw materials in percentage by weight:
Figure BDA0003037894310000031
Figure BDA0003037894310000041
the preparation method of the wet flue gas desulfurization solid synergist comprises the following steps:
(1) weighing water according to the concentration of 20 percent (g/ml) of povidone, sequentially adding 600g of sodium citrate and 80g of povidone into the water, and stirring to dissolve the sodium citrate and the povidone to obtain an adhesive solution for later use;
(2) 220g of sodium dioctyl sulfosuccinate and 100g of magnesium sulfate were added to the fluidized bed and preheated, and spraying of the binder solution obtained in step (1) was started when the material temperature reached 42 ℃.
(3) And (5) after the liquid spraying is finished. Drying until LOD and acetic acid residue of the product are lower than quality standard to obtain dry granules.
(4) And (4) granulating the obtained dry particles by using a granulator to obtain the target product.
The raw material povidone used in this example is polyvinylpyrrolidone (PVP), which is a chemical name, and is obtained by bulk polymerization, solution polymerization, or the like using vinyl pyrrolidone (NVP) as a monomer as a raw material. PVP is classified into four grades based on its average molecular weight, which is conventionally represented by the K value, with different K values representing the respective PVP average molecular weight ranges. The K value is actually a characteristic value related to the relative viscosity of the aqueous solution of PVP, which in turn is a physical quantity related to the molecular weight of the high polymer, and thus the K value can be used to characterize the average molecular weight of PVP. In general, the larger the K value, the higher the viscosity, and the stronger the adhesiveness. PVP is used as a synthetic water-soluble polymer compound, has the general properties of the water-soluble polymer compound, and has the advantages of colloid protection effect, film-forming property, cohesiveness, hygroscopicity, solubilization or condensation effect, excellent solubility and physiological compatibility, and the PVP is soluble in water and most of organic solvents, and has low toxicity and good physiological compatibility.
Example 2
A solid synergist for wet flue gas desulfurization is prepared from the following raw materials in percentage by weight:
Figure BDA0003037894310000042
Figure BDA0003037894310000051
the preparation method of the wet flue gas desulfurization solid synergist comprises the following steps:
(1) weighing water according to the concentration of the povidone of 22.5 percent (g/ml), sequentially adding 780g of adipic acid and 20g of povidone into the water, and stirring to dissolve the materials to obtain an adhesive solution for later use;
(2) 100g of sodium dioctyl sulfosuccinate and 100g of calcium sulfate were introduced into the fluidized bed and preheated, and spraying of the binder solution obtained in step (1) was started when the batch temperature reached 42 ℃.
(3) And (5) after the liquid spraying is finished. Drying until LOD and acetic acid residue of the product are lower than quality standard to obtain dry granules.
(4) And (4) granulating the obtained dry particles by using a granulator to obtain the target product.
The adipic acid used as a raw material in this embodiment is also referred to as adipic acid, and is an important organic dibasic acid, which can undergo a salt formation reaction, an esterification reaction, an amidation reaction, and the like, and can be polycondensed with diamine or diol to form a high-molecular polymer, and the like.
Example 3
A solid synergist for wet flue gas desulfurization is prepared from the following raw materials in percentage by weight:
Figure BDA0003037894310000052
Figure BDA0003037894310000061
the preparation method of the wet flue gas desulfurization solid synergist comprises the following steps:
(1) weighing glacial acetic acid according to the concentration of 20% (g/ml) of povidone, sequentially adding 600g of adipic acid and 50g of povidone into the glacial acetic acid, and stirring to dissolve the mixture to obtain an adhesive solution for later use;
(2) 250g of sodium dioctyl sulfosuccinate and 100g of calcium sulfate were introduced into the fluidized bed and preheated, and spraying of the binder solution obtained in step (1) was started when the batch temperature reached 42 ℃.
(3) And (5) after the liquid spraying is finished. Drying until LOD and acetic acid residue of the product are lower than quality standard to obtain dry granules.
(4) And (4) granulating the obtained dry particles by using a granulator to obtain the target product.
The calcium carbonate used as a raw material in this example was white monoclinic crystal or crystalline powder, and had no odor and hygroscopicity. Losing 1 molecule of crystal water at 128 ℃ and losing all water at 163 ℃. Dissolving in acid, sodium thiosulfate and ammonium salt solution, and dissolving in 400 parts
Water, which dissolves less in hot water, dissolves very slowly in glycerol, and is practically insoluble in ethanol and most organic solvents. The relative density was 2.32. Has irritation.
The solid synergist for wet flue gas desulfurization provided by the embodiment has the following technical effects:
1. the wet flue gas desulfurization solid synergist provided by the embodiment has the advantages of small particle size, more gaps and large specific surface area, and can greatly improve the desulfurization efficiency, so that the dosage of the synergist is less.
2. The solid synergist for wet flue gas desulfurization provided by the embodiment has the advantages of quick effect, low consumption and simple formula, reduces the cost on the whole and has certain economic benefit.
3. The preparation method of the solid synergist for wet flue gas desulfurization provided by the embodiment adopts a wet granulation technology to prepare the synergist, the method is simple, the process reproducibility is good, and the components in the produced product are uniformly distributed.
Example 4
A solid synergist for wet flue gas desulfurization is prepared from the following raw materials in percentage by weight:
Figure BDA0003037894310000062
Figure BDA0003037894310000071
the preparation method of the wet flue gas desulfurization solid synergist comprises the following steps:
(1) weighing water according to the concentration of 20 percent (g/ml) of povidone, sequentially adding 600g of sodium citrate and 50g of povidone into the water, and stirring to dissolve the sodium citrate and the povidone to obtain an adhesive solution for later use;
(2) 150g of sodium dioctyl sulfosuccinate and 200g of magnesium sulfate were added to the fluidized bed and preheated, and spraying of the binder solution obtained in step (1) was started when the material temperature reached 42 ℃.
(3) And (5) after the liquid spraying is finished. Drying until LOD and acetic acid residue of the product are lower than quality standard to obtain dry granules.
(4) And (4) granulating the obtained dry particles by using a granulator to obtain the target product.
The raw material sodium citrate used in this example, also known as sodium citrate, is an organic compound and is white to colorless crystal in appearance. No odor, and cool, salty and spicy taste. Stable at normal temperature and in air, has slight solubility in humid air, and generates weathering phenomenon in hot air. Heating to 150 ℃ lost the water of crystallization. Is easily soluble in water, soluble in glycerol, and insoluble in alcohols and other organic solvents, and can be decomposed by overheating, deliquesced slightly in humid environment, and weathered slightly in hot air, and the pH value of the solution is about 8.
The desulfurization synergy research results are as follows:
at an inlet sulfur dioxide concentration of>2000mg/m3The desulfurization rates of limestone-gypsum wet flue gas desulfurization systems without the addition of the synergist of the present invention and systems with the addition of the synergist described in examples 1-4 of the present invention are shown in the following table.
Table 1: desulfurization rate comparison data table
Figure BDA0003037894310000072
It can be seen from the data in the table that, after the solid synergist for wet flue gas desulfurization obtained in examples 1-4 is added into a limestone-gypsum wet flue gas desulfurization system according to 20mg/L, the sulfur dioxide concentration at the outlet is respectively reduced from 2689 to 53.78, 2429 to 73, 2097 to 83.88, and 2865 to 86, and the desulfurization rates are respectively 98%, 97%, 96%, and 97%, whereas the desulfurization rate is only 82% without adding the invention into the limestone-gypsum wet flue gas desulfurization system, it can be obviously found that the desulfurization rate is significantly improved after adding the synergist of the invention, and all can reach the latest national emission standard, the sulfur dioxide concentration at the outlet of the solid synergist for wet flue gas desulfurization obtained in example 3 with 50mg/L added into the limestone-gypsum wet flue gas desulfurization system is reduced from 2827 to 28.27, and the desulfurization efficiency is 99%, it can be seen that within a suitable range, the desulfurization rate is increased with the increase in the amount of the enhancer of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
In the context of the present invention, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used. There may be differences below 10% in the value of each number or reasonably considered by those skilled in the art, such as differences of 1%, 2%, 3%, 4% or 5%.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The solid synergist for wet flue gas desulfurization is characterized by comprising the following components in percentage by weight: 60% -80% of buffering agent, 10% -25% of surfactant, 10% -20% of inorganic salt and 2% -8% of adhesive.
2. The wet flue gas desulfurization solid synergist according to claim 1, wherein the buffer comprises one or more of citric acid, sodium citrate, succinic acid, adipic acid, tartaric acid, ascorbic acid, benzoic acid, and malic acid.
3. The wet flue gas desulfurization solid synergist according to claim 2, wherein the surfactant comprises one or more of stearic acid, sodium dodecylbenzene sulfonate, and sodium dioctyl sulfosuccinate.
4. The wet flue gas desulfurization solid synergist according to claim 3, wherein the inorganic salt is one or more of sodium chloride, potassium carbonate, potassium oxalate, magnesium sulfate, and calcium sulfate.
5. The wet flue gas desulfurization solid synergist according to claim 4, wherein the binder is one or more of pregelatinized gelatin, povidone, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, powdered sugar, starch slurry, and gelatin.
6. The wet flue gas desulfurization solid synergist according to claim 5, wherein the binder is povidone.
7. The wet flue gas desulfurization solid synergist according to claim 6, wherein the binder is povidone K29/32.
8. The wet flue gas desulfurization solid synergist according to claim 7, wherein D of the wet flue gas desulfurization solid synergist is90≤100μm。
9. The method for preparing the solid synergist for wet flue gas desulfurization according to any one of claims 1 to 8, comprising the steps of:
dissolving a buffering agent and an adhesive in water, and uniformly stirring to obtain an adhesive solution for later use;
adding a surfactant and an inorganic salt into a fluidized bed for preheating, and spraying the adhesive solution when the temperature of the surfactant and the inorganic salt reaches 35-50 ℃;
after the spraying is finished, drying to obtain dry particles;
and (4) finishing the dry particles.
10. The method for preparing the solid synergist for wet flue gas desulfurization according to claim 9, wherein the binder solution is sprayed at an atomization pressure of 0.5bar to 2.0bar and a spraying speed of 3.0g/min to 20.0 g/min.
CN202110448572.6A 2021-04-25 2021-04-25 Wet flue gas desulfurization solid synergist and preparation method thereof Pending CN113117512A (en)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
EP0578363A1 (en) * 1992-07-06 1994-01-12 Sumitomo Heavy Industries, Ltd Method for operating dry-process, desulfurization apparatus
CN101569828A (en) * 2009-06-10 2009-11-04 河北工业大学 Solid particle used for jetting bed flue gas desulfurization process and preparation method
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CN102814118A (en) * 2012-09-17 2012-12-12 上海电力学院 Flue gas desulfurization additive, and preparation method and application thereof
CN103263842A (en) * 2013-06-18 2013-08-28 上海电力学院 Flue gas desulfurization synergist in wet desulfurization system as well as preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
EP0578363A1 (en) * 1992-07-06 1994-01-12 Sumitomo Heavy Industries, Ltd Method for operating dry-process, desulfurization apparatus
CN101569828A (en) * 2009-06-10 2009-11-04 河北工业大学 Solid particle used for jetting bed flue gas desulfurization process and preparation method
CN102580514A (en) * 2012-02-29 2012-07-18 济宁新格瑞水处理有限公司 Additive for strengthening wet flue gas desulfurization technology
CN102814118A (en) * 2012-09-17 2012-12-12 上海电力学院 Flue gas desulfurization additive, and preparation method and application thereof
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