CN107399753B - Device and method for oxidative modification of sintering semi-dry desulfurization ash - Google Patents

Device and method for oxidative modification of sintering semi-dry desulfurization ash Download PDF

Info

Publication number
CN107399753B
CN107399753B CN201710123582.6A CN201710123582A CN107399753B CN 107399753 B CN107399753 B CN 107399753B CN 201710123582 A CN201710123582 A CN 201710123582A CN 107399753 B CN107399753 B CN 107399753B
Authority
CN
China
Prior art keywords
oxygen
desulfurization ash
solution
agent
ash
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710123582.6A
Other languages
Chinese (zh)
Other versions
CN107399753A (en
Inventor
王毅璠
龙红明
魏汝飞
李家新
王平
孟庆民
春铁军
狄瞻霞
余正伟
钱立新
张行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui University of Technology AHUT
Original Assignee
Anhui University of Technology AHUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui University of Technology AHUT filed Critical Anhui University of Technology AHUT
Priority to CN201710123582.6A priority Critical patent/CN107399753B/en
Publication of CN107399753A publication Critical patent/CN107399753A/en
Application granted granted Critical
Publication of CN107399753B publication Critical patent/CN107399753B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a sintering semi-dry typeAn oxidation modification device and an oxidation modification method for desulfurization ash, belonging to the field of desulfurization ash recycling application. The oxygen-assisted agent injection unit comprises an oxygen-assisted agent container and a liquid pipeline, wherein the oxygen-assisted agent container is communicated with the liquid pipeline, and is used for injecting an oxygen-assisted agent solution into the mixed liquid of the desulfurization ash, and when oxygen-containing gas is blown into the mixed liquid of the desulfurization ash and water, the oxygen-assisted agent is mixed with the water through the combined action of the reaction unit, the air supply unit and the oxygen-assisted agent injection unit to obtain oxygen-assisted agent solution; and uniformly injecting an oxygen-assisting agent solution into the bottom of the desulfurization ash mixed solution, wherein the oxygen-assisting agent comprises an acidic auxiliary agent and the pKa of the acidic auxiliary agent 1 The acidity coefficient is between the pKa of sulfurous acid and sulfuric acid 1 The acidity coefficient. The oxidation modification method of the invention accelerates the oxidation efficiency of the desulfurization ash by changing the reaction interface in the oxidation process of the desulfurization ash, and lays a foundation for the recycling application of the desulfurization ash.

Description

Device and method for oxidative modification of sintering semi-dry desulfurization ash
Technical Field
The invention relates to the field of desulfurization ash recycling application, in particular to a device and a method for oxidative modification of desulfurization ash by a sintering semi-dry method.
Background
The total yield of the global coarse steel in 2016 reaches 16.285 hundred million tons, and the global coarse steel is increased by 0.8 percent in the same ratio; wherein the crude steel yield of China is 8.084 hundred million tons (49.6 percent of the global crude steel yield), and the comparability is still increased by 1.2 percent. The sintering process is an important link in the modern steel production flow and is also a main pollutant emission source in the steel industry, wherein the SO of the steel industry is more than 70 percent 2 From the sintering process. SO is introduced into the latest revised' pollution emission standard of the iron and steel industry 2 As one of important contents, the emission control of the steel industry is mandatory to realize emission reduction and standard emission of flue gas in a limited period. SO discharged by iron and steel enterprises in China 2 50% -70% of the desulfurization process comes from the sintering process, and the semi-dry desulfurization technology is adopted to carry out sintering flue gas desulfurization, so that the investment is low, the desulfurization rate is high, a large amount of desulfurization ash is generated in the semi-dry desulfurization process, only a small amount of desulfurization ash is utilized at home and abroad, most of the desulfurization ash is discarded, and if the desulfurization ash is not reasonably utilized, secondary pollution is caused and a large amount of land is occupied.
With the enhancement of environmental protection consciousness in China, research on comprehensive utilization of the sinter flue gas desulfurization ash is gradually focused by people, and the utilization of the sinter flue gas desulfurization ash can reduce funds consumed by stacking, occupy land and environmental pollution, reduce the consumption of natural gypsum, further reduce the exploitation amount of the natural gypsum and protect ecological environment. Therefore, many universities and enterprises have conducted a great deal of research on comprehensive utilization of the flue gas desulfurization ash of the sinter, such as preparation of sulfuric acid, cement retarder, gypsum building material, calcium sulfate whisker and the like by using the flue gas desulfurization ash of the sinter. The calcium sulfate whisker prepared by sintering flue gas desulfurization ash has higher added value, is a short fiber grown in a single crystal form, has uniform cross section, complete appearance and highly perfect internal structure, and has the advantages of extremely high strength and fine size compared with glass fiber, is easier to combine with organic high polymer compounds such as resin, rubber, plastic and the like, and has excellent appearance quality. Can be widely used in various fields of automobiles, aerospace, chemical industry, metallurgy, national defense, machinery, electricity, ships, petroleum, building materials and the like. The preparation of the calcium sulfate whisker by taking the desulfurized gypsum as the raw material not only can reduce the pollution of the desulfurized gypsum to the environment, but also can save natural gypsum resources, and opens up a new way for the high added value utilization of the desulfurized gypsum, but the existing method for preparing the calcium sulfate whisker by using the desulfurized ash is still imperfect, so that the quality of the calcium sulfate whisker is poor, and the high-efficiency recycling application of the desulfurized ash is severely limited.
The patent search shows that Shi Peiyang of northeast university is subjected to prior research and related patents are applied for, and a method for preparing calcium sulfate whiskers by using sintering ore flue gas desulfurization byproducts (application number: 201010545829.1; application date: 2010.11.16) and a method for preparing calcium sulfate whiskers by using flue gas desulfurization gypsum (application number: 200810011193.5; application date: 2008.04.25) provide a way for recycling the desulfurization ash. In addition, a process and a device for preparing gypsum whisker by using semi-dry desulfurization ash and waste acid (application number: 201210405335.2, application date: 2012.10.22) realize the recycling application of the desulfurization ash. However, the quality of the calcium sulfate whisker produced by the existing method is poor, and the high added value application of the desulfurization ash is limited. In addition, the applicant has obtained a series of breakthrough tension after long-time exploration before the present time, and applied for an invention patent, namely a flue gas desulfurization ash modification treatment method (application number: 201611068316X) and a flue gas desulfurization ash low-temperature oxidation device (application number: 2016110682881), which have remarkable effects on modification of desulfurization ash; after that, the invention breaks the original technical thought, reconstructs a brand-new desulfurization ash treatment device and a brand-new desulfurization ash treatment method, develops a brand-new acid oxidation method based on oxidation of an oxygen-assisting agent, and promotes the recycling application of desulfurization ash.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problem of poor oxidation efficiency of semi-dry desulfurization in the prior art, and provides a device and a method for modifying the oxidation of sintering semi-dry desulfurization ash;
according to the sintering semi-dry desulfurization ash oxidation device, through the combined action of the reaction unit, the air supply unit and the oxygen-assisting agent injection unit, an oxygen-assisting agent solution is uniformly injected into the bottom of the desulfurization ash mixed liquid, and the oxygen-assisting agent can change a reaction interface in the desulfurization ash oxidation process, so that the oxidation efficiency of desulfurization ash can be accelerated;
according to the method for oxidizing the desulfurization ash by using the oxidation device, the oxygen-assisting agent solution is uniformly injected into the bottom of the desulfurization ash mixed solution, and the oxygen-assisting agent can change the reaction interface in the oxidation process of the desulfurization ash, so that the oxidation efficiency of the desulfurization ash can be accelerated; further, the purity of the calcium sulfate dihydrate in the reaction product can be improved.
2. Technical proposal
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the invention relates to a sintering semi-dry desulfurization ash oxidation device, which comprises a reaction unit, wherein the reaction unit comprises a reactor inner cavity, and the reactor inner cavity is used for containing oxidized desulfurization ash mixed solution; the gas pipeline of the gas supply unit extends into the bottom of the inner cavity of the reactor, and the gas supply unit is used for blowing oxygen-containing gas into the desulfurization ash mixed liquid; and the oxygen-assisting agent injection unit comprises an oxygen-assisting agent container and a liquid pipeline, wherein the oxygen-assisting agent container is communicated with the liquid pipeline, and the oxygen-assisting agent injection unit is used for injecting an oxygen-assisting agent solution into the desulfurization ash mixed liquid.
Preferably, the liquid pipeline stretches into the bottom of the inner cavity of the reactor, a liquid outlet is arranged at the bottom of the liquid pipeline, an air pipe outlet of the gas pipeline is arranged corresponding to the liquid outlet, and the air pipe outlet is sprayed towards the liquid outlet.
Preferably, the liquid pipeline extends into the gas pipeline, and the oxygen-assisting agent solution in the oxygen-assisting agent container enters the bottom of the inner cavity of the reactor under the driving of the gas supply unit.
Preferably, a bubble generator is arranged at the bottom of the liquid pipeline, and the bubble generator enables the gas and the oxygen-aid solution to be uniformly distributed in the inner cavity of the reactor.
Preferably, a constant temperature outer cavity is arranged outside the inner cavity of the reactor, and the constant temperature outer cavity is used for keeping the inner cavity of the reactor at a constant temperature.
The invention relates to a method for oxidizing desulfurization ash by using an oxidation device, which comprises the following specific steps:
s1, removing impurities and drying
Mixing the desulfurized ash raw material with water, removing large-particle insoluble substances through a water screen, and vacuum filtering to obtain desulfurized ash after impurity removal;
s2, preparing a desulfurization ash solution
Mixing the desulfurization ash obtained in the step S1 with deionized water, wherein the solid-to-liquid ratio of the desulfurization ash to the deionized water is 1/20-1/50, and sufficiently oscillating to obtain a desulfurization ash mixed solution;
s3, desulphurized ash acid oxidation
(1) The mass ratio of the oxygen-assisting agent to the filtered and decontaminated desulfurization ash is 0.2-0.3, the oxygen-assisting agent is dissolved in deionized water to obtain an oxygen-assisting agent solution, and then the oxygen-assisting agent solution is added into an oxygen-assisting agent container of a desulfurization ash oxidation device, wherein the oxidation device is the oxidation device of any one of claims 1-5; the oxygen-assisting agent comprises an acidic auxiliary agent, and the pKa of the acidic auxiliary agent 1 The acidity coefficient is between the pKa of sulfurous acid and sulfuric acid 1 The oxygen-assisting agent is used for oxidizing calcium sulfite in the desulfurization ash between acidity coefficients;
(2) Adding the desulfurization ash mixed solution into the inner cavity of the reactor, opening an inner cavity stirrer, blowing oxygen-containing gas into the desulfurization ash mixed solution, uniformly injecting an oxygen-assisting agent solution in an oxygen-assisting agent container into the bottom of the desulfurization ash mixed solution in the process of oxidizing the desulfurization ash, and obtaining oxidized desulfurization ash.
Preferably, the time of the oxidation reaction of the desulfurized ash mixed liquid in the step (2) is 80-150min, and the time of the injection of the oxygen-assisting agent solution is the same as the time of the reaction.
Preferably, the acidic auxiliary is readily soluble in water, the acidic auxiliary having a pKa in water at 25 DEG C 1 The acidity coefficient is: 1.00-1.89.
Preferably, the acid auxiliary agent is oxalic acid or dichloroacetic acid or a combination of the oxalic acid and dichloroacetic acid.
Preferably, the oxygen-assisting agent also comprises an additive, wherein the oxygen-assisting agent comprises the following components in parts by mass:
10-20 parts of an acidic auxiliary agent;
8-12 parts of additive;
wherein the additive comprises citric acid triamine and pyruvic acid.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) The invention relates to a method for oxidizing desulfurization ash by using an oxidation device, which is characterized in that an oxygen-assisting agent solution is uniformly injected into the bottom of a desulfurization ash mixed solution, and the pKa of an acidic auxiliary agent in the oxygen-assisting agent 1 The acidity coefficient is between the pKa of sulfurous acid and sulfuric acid 1 The acidity coefficient changes the reaction interface in the oxidation process of the desulfurization ash, so that the oxidation efficiency of the desulfurization ash can be accelerated, and meanwhile, the reaction energy consumption is reduced, so that the economic benefit of industrial production is improved;
(2) The invention relates to a method for oxidizing desulfurization ash by an oxidation device, which comprises the step of adding an oxygen-assisting agent into CaSO in the desulfurization ash 3 The ionic state is formed to enter the solution, the reaction interface in the oxidation process of the desulfurization ash is changed, the oxidation of the desulfurization ash in the open condition is realized, and simultaneously, the oxygen-assisting agent is slowly and uniformly added easily, SO that SO is effectively avoided 2 Escape of (2);
(3) According to the method for oxidizing the desulfurization ash by using the oxidation device, the content of calcium sulfate dihydrate in a reaction product after the desulfurization ash is oxidized is greatly improved, and the purity of the calcium sulfate dihydrate in the dry powder is higher, which is equivalent to purifying the desulfurization ash in the oxidation process, so that a foundation is laid for the subsequent preparation of whiskers;
(4) According to the sintering semi-dry desulfurization ash oxidation device, through the combined action of the reaction unit, the air supply unit and the oxygen-assisting agent injection unit, the oxygen-assisting agent solution is uniformly injected into the bottom of the desulfurization ash mixed solution, and the oxygen-assisting agent can change the reaction interface in the desulfurization ash oxidation process, so that the oxidation efficiency of desulfurization ash can be accelerated;
(5) The invention relates to a sintering semi-dry desulfurization ash oxidation deviceThe flow control valve is used for controlling the adding speed of the oxygen-assisting agent solution, so as to regulate and control the adding time of the oxygen-assisting agent solution, ensure that the injecting time of the oxygen-assisting agent solution is the same as the reaction time, and the oxygen-assisting agent solution is slowly and uniformly injected into the bottom of the desulfurization ash mixed solution all the time, and CaSO in the desulfurization ash is added after the oxygen-assisting agent is added 3 Forming ionic state into solution while avoiding SO 2 Escape of (2);
(6) According to the sintering semi-dry desulfurization ash oxidation device, the air pipe outlet of the air pipe is correspondingly arranged with the liquid outlet, and the air pipe outlet is sprayed towards the liquid outlet, so that the oxygen-assisting agent solution is CaSO in the desulfurization ash in the process of combining the desulfurization ash 3 After the ion state is formed into the solution, the oxygen-containing gas can quickly react with the H in the solution state 2 SO 3 Bind and undergo oxidation to form SO 4 2- Thereby accelerating the reaction rate.
Drawings
FIG. 1 is a schematic view showing the structure of an oxidizing apparatus according to embodiment 1 of the present invention;
FIG. 2 is a schematic structural view of an oxidation device according to embodiment 2 of the present invention;
fig. 3 is a schematic structural view of an oxidation apparatus according to embodiment 3 of the present invention.
Reference numerals in the drawings illustrate:
100. a reaction unit; 110. a reactor cavity; 111. an inner cavity stirrer; 112. a thermocouple; 120. a constant temperature outer chamber; 121. a refrigerant inlet; 122. a refrigerant outlet;
200. an air supply unit; 210. a gas supply cylinder; 211. an outlet of the gas cylinder; 212. a gas cooling mechanism; 220. a gas control valve; 221. a valve inlet; 230. a flow meter; 240. a gas conduit; 241. an air tube outlet; 242. a bubble generator;
300. an oxygen-aid injection unit; 310. an oxygen-aid container; 320. a flow control valve; 330. a liquid conduit; 331. and a liquid outlet.
Detailed Description
The following detailed description of exemplary embodiments of the invention, while these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely illustrative and not limiting of the invention's features and characteristics in order to set forth the best mode of carrying out the invention and to sufficiently enable those skilled in the art to practice the invention. Accordingly, the scope of the invention is limited only by the attached claims.
Example 1
As shown in fig. 1, the sintering semi-dry desulfurization ash oxidation apparatus of the present invention comprises a reaction unit 100, an air supply unit 200 and an oxygen-assisted agent injection unit 300, wherein the reaction unit 100 comprises a reactor cavity 110, the reactor cavity 110 is used for containing oxidized desulfurization ash mixed solution, an inner cavity stirrer 111 is arranged in the middle of the reactor cavity 110, and the inner cavity stirrer 111 is used for stirring the desulfurization ash mixed solution in the reactor cavity 110 to promote the homogenization of the reaction; a thermocouple 112 is provided on the reactor cavity 110 for monitoring the temperature of the mixed liquor within the reactor cavity 110. The gas supply unit 200 includes a gas supply bottle 210, a gas control valve 220, a flow meter 230 and a gas pipe 240, the gas supply bottle 210 is connected to the gas pipe 240 through the gas control valve 220, a gas bottle outlet 211 of the gas supply bottle 210 is connected to a valve inlet 221 of the gas control valve 220, the other end of the gas control valve 220 is connected to the gas pipe 240, the flow meter 230 is disposed on the gas pipe 240, the flow meter 230 can detect the flow rate of the blown gas, the gas pipe 240 stretches into the bottom of the reactor cavity 110, the gas supply unit 200 is used for blowing oxygen-containing gas into the mixed liquid of the desulfurization ash, and the stirring of the desulfurization ash solution is enhanced by blowing the oxygen-containing gas into the bottom of the reactor cavity 110, so that the reaction is promoted, and the oxidation reaction of the desulfurization ash is accelerated.
The oxygen-aid injection unit 300 of the present embodiment is used for injecting an oxygen-aid solution into a desulfurization ash mixture, and the oxygen-aid injection unit 300 includes an oxygen-aid container 310, a flow control valve 320 and a liquid pipe 330, wherein the oxygen-aid container 310 is connected with the liquid pipe 330The flow control valve 320 is arranged on the liquid pipeline 330, and the flow control valve 320 is used for controlling the adding speed of the oxygen-aid solution, so as to regulate and control the adding time of the oxygen-aid solution, thereby ensuring that the injecting time of the oxygen-aid solution is the same as the reaction time, namely, the oxygen-aid solution is always slowly and uniformly injected into the bottom of the desulfurization ash mixed solution from the beginning of the reaction to the end of the reaction, and CaSO in the desulfurization ash is added after the oxygen-aid is added 3 Forming ionic state into solution while avoiding SO 2 Has significant progress.
The liquid pipe 330 of the embodiment extends into the bottom of the reactor cavity 110, a liquid outlet 331 is arranged at the bottom of the liquid pipe 330, a gas pipe outlet 241 of the gas pipe 240 is arranged corresponding to the liquid outlet 331, and the gas pipe outlet 241 is sprayed towards the liquid outlet 331, so that the oxygen-assisting agent solution is CaSO in the desulfurization ash combining process 3 After the ion state is formed into the solution, the oxygen-containing gas can quickly react with the H in the solution state 2 SO 3 Bind and undergo oxidation to form SO 4 2- Thereby accelerating the reaction rate.
The outside of the reactor cavity 110 of this embodiment is provided with a constant temperature external cavity 120, the constant temperature external cavity 120 is used for keeping the reactor cavity 110 at a constant temperature, the constant temperature external cavity 120 can be an electric control constant temperature box, and can also be a constant temperature external cavity 120 for injecting a refrigerant, one side of the constant temperature external cavity 120 is provided with a refrigerant inlet 121, the other side corresponding to the constant temperature external cavity is provided with a refrigerant outlet 122, the level of the refrigerant outlet 122 is higher than that of the refrigerant inlet 121, and a cooling medium enters from the refrigerant inlet 121 and flows out from the refrigerant outlet 122 to cool the reactor cavity 110.
The invention relates to a method for oxidizing desulfurization ash by an oxidation device, wherein the used oxygen promoter comprises an acid auxiliary agent, the acidity of the acid auxiliary agent is between that of sulfurous acid and sulfuric acid, namely the pKa of the acid auxiliary agent 1 The acidity coefficient is between the pKa of sulfurous acid and sulfuric acid 1 Between acidity coefficients, the oxygen-assisting agent is used for oxidizing calcium sulfite in the desulfurization ash, the acid auxiliary agent is easy to dissolve in water, and the acid auxiliary agent is water at 25 DEG CpKa of (b) 1 The acidity coefficient is: 1.00-1.89, wherein said pKa 1 The first order acidity coefficient of the acid promoter in this example is oxalic acid, its pKa 1 1.27; the oxygen-assisting agent in this embodiment is oxalic acid, and the oxalic acid is mixed with water to obtain an oxygen-assisting agent solution. Wherein: the acidity coefficient (pKa), also known as the acid dissociation constant, is the opposite of the usual logarithm of the acid dissociation equilibrium constant, defined by the formula pka= -lg (Ka).
And mixing the desulfurized ash with water to obtain a desulfurized ash mixed solution, and injecting an oxalic acid solution into the mixed solution, wherein the mass ratio of the oxygen-assisting agent to the desulfurized ash after filtering and impurity removal is 0.2-03, namely the mass ratio of pure oxalic acid powder to the desulfurized ash is 0.2-0.3.
As shown in fig. 1, the method for oxidizing desulfurization ash by using the oxidation device comprises the following specific steps:
s1, removing impurities and drying
Mixing the desulfurized ash raw material with water, removing large-particle insoluble matters on a sieve through a 200-mesh water sieve, obtaining desulfurized ash after impurity removal through vacuum suction filtration, and then placing the desulfurized ash into a drying oven for drying for 4 hours at 105 ℃;
s2, preparing a desulfurization ash solution
Mixing 20g of the desulfurized fly ash obtained in the step S1 with deionized water, wherein the solid-to-liquid ratio of the desulfurized fly ash to the deionized water is 1/50, and placing the mixture into a gas bath vibration box to sufficiently vibrate for 30min at 50 ℃ to obtain a desulfurized fly ash mixed solution;
s3, desulphurized ash acid oxidation
(1) The mass ratio of the oxygen-assisting agent to the filtered and decontaminated desulfurization ash is 0.2-0.3, in the embodiment, 0.2 is taken, 4g of the oxygen-assisting agent is dissolved in deionized water to obtain an oxygen-assisting agent solution, the mass ratio of the oxygen-assisting agent to the deionized water is 0.05-0.2, in the embodiment, 0.05 is preferred to obtain 84g of the oxygen-assisting agent solution, and the oxygen-assisting agent solution is added into an oxygen-assisting agent container 310;
(2) Adding the desulfurized fly ash mixed solution into the reactor inner cavity 110, controlling the constant temperature of the constant temperature outer cavity 120, keeping the temperature in the reactor inner cavity 110 at 5 ℃, opening the gas control valve 220 of the gas supply unit 200 to blow oxygen-containing gas into the desulfurized fly ash mixed solution, and controlling the temperature of the constant temperature outer cavity 120 to be 5 ℃ in the reactor inner cavityIs air; simultaneously, a flow control valve 320 of an oxygen-aid injection unit 300 is opened, an oxygen-aid solution is injected into the bottom of the inner cavity 110 of the reactor from an oxygen-aid container 310 through a liquid pipeline 330, the oxygen-aid solution is uniformly injected into the bottom of the desulfurization ash mixed solution in the process of oxidizing desulfurization ash, and the reaction time is 150min; in the reaction process, the blowing flow of the oxygen-containing gas regulated and controlled by the gas control valve 220 and the flowmeter 230 is 15ml/min, the gas pipe outlet 241 of the gas pipeline 240 is arranged corresponding to the liquid outlet 331, and the gas pipe outlet 241 is sprayed towards the liquid outlet 331, so that the oxygen-assisting agent solution is CaSO in the desulfurization ash combination process 3 After the ion state is formed into the solution, the oxygen-containing gas can quickly react with the H in the solution state 2 SO 3 Bind and undergo oxidation to form SO 4 2- Thereby accelerating the reaction rate; the oxidation modification of the desulfurized fly ash is also referred to as oxidation, since the modification treatment of the desulfurized fly ash in the present invention is an oxidation treatment of desulfurization. Noteworthy are: the injection time of the oxygen-assisting agent solution is the same as the reaction time, namely, the oxygen-assisting agent solution is slowly and uniformly injected into the bottom of the desulfurization ash mixed solution all the time from the beginning of the reaction to the end of the reaction, namely, 84g of the oxygen-assisting agent solution is slowly and uniformly injected in the reaction time of 150 min. And after the reaction is finished, reactant precipitate is obtained, the precipitate is heated and dried at the temperature of 100 ℃ to obtain dry powder, the content of calcium sulfate dihydrate in the dry powder reaches 96.1%, the purity of the calcium sulfate dihydrate in a reaction product is improved, and the purity of the calcium sulfate dihydrate is equivalent to the purity of the calcium sulfate dihydrate in the desulfurization ash oxidation process, so that a foundation is laid for the subsequent preparation of whiskers.
In order to oxidize calcium sulfite in the desulfurization ash, the prior art often adds an oxidizing agent to the desulfurization ash mixed solution under a closed condition of high temperature (about 300 ℃) and high pressure to oxidize the calcium sulfite in the desulfurization ash. Although this method has a certain effect on the oxidation treatment of the desulfurized fly ash. However, the flue gas desulfurization ash obtained by semi-dry sintering is relatively complex in composition, contains a large amount of calcium sulfite, and also contains part of calcium sulfate, residual calcium oxide, calcium carbonate and the like,although some researches show that the desulfurization ash oxidation method has a certain oxidation effect, impurities in a desulfurization product cannot be removed; in an open reactor, it is often difficult to achieve CaSO in an open reactor due to the low solubility of sulfurous acid in water 3 Therefore, in the prior art, high-temperature and high-pressure airtight conditions are often adopted to perform oxidation first, thereby avoiding SO 2 Escape. In addition, the products obtained by oxidation are high in oxidation cost and low in efficiency, the purity of the products obtained by oxidation is poor, and the higher oxidation temperature greatly increases the energy consumption of industrial application and seriously influences the recycling application of the desulfurization ash.
The invention breaks the technical bias of the prior art, and in the oxidation reaction process, the oxidation of the desulfurization ash in the open condition is realized by slowly adding the oxygen-assisting agent into the desulfurization ash mixed solution, wherein the oxygen-assisting agent in the embodiment is oxalic acid, and CaSO in the desulfurization ash is obtained after the oxygen-assisting agent is added 3 Form ion state to enter solution, effectively avoid SO 2 And H is generated in the solution 2 SO 3 Thereby changing the reaction interface in the oxidation process of the desulfurization ash, carrying out ion reaction oxidation, further accelerating the oxidation reaction of the desulfurization ash, selecting oxalic acid as an oxygen-assisting agent to improve the oxidation degree of the desulfurization ash, and simultaneously effectively avoiding SO 2 Is not limited. Meanwhile, the invention creatively provides low-temperature oxidation (the temperature of the oxidation process of the embodiment is maintained at 5 ℃), in order to increase the oxidation rate under normal conditions, the prior researchers tend to consciously increase the reaction temperature and further increase the reaction rate, but the invention greatly improves the reaction efficiency by reducing the reaction temperature and improving the reaction interface in the oxidation process of calcium sulfite, and achieves unexpected effects, and the invention has unobvious and outstanding substantive characteristics and remarkable progress.
Comparative example 1
The basic content of this comparative example was the same as in example 1, except that the experimental apparatus of example 1 was not employed, the reaction time was 180 minutes after the completion of the reaction to obtain a precipitate, and the precipitate was heated and dried at 100℃to obtain a dry powder, the calcium sulfate dihydrate content in the dry powder reaching 95.2%.
It can be found that the calcium sulfate dihydrate content of example 1 is further increased and the reaction efficiency is accelerated as compared with comparative example 1; the reason for this is that: the flow control valve 320 is adopted to regulate the adding time of the oxygen-assisting agent solution, so that the injection time of the oxygen-assisting agent solution is identical with the reaction time, namely, the oxygen-assisting agent solution is slowly and uniformly injected into the bottom of the desulfurization ash mixed solution from the beginning of the reaction to the end of the reaction, and CaSO in the desulfurization ash is added after the oxygen-assisting agent is added 3 Forming ionic state into solution while avoiding SO 2 Escape of (2); and the gas pipe outlet 241 of the gas pipe 240 is arranged corresponding to the liquid outlet 331, and the gas pipe outlet 241 is sprayed towards the liquid outlet 331, so that the oxygen-assisting agent solution is CaSO in the desulfurization ash in the process of combining the desulfurization ash 3 After the ion state is formed into the solution, the oxygen-containing gas can quickly react with the H in the solution state 2 SO 3 Bind and undergo oxidation to form SO 4 2- Thereby accelerating the reaction rate.
Example 2
The basic content of this embodiment is the same as embodiment 1, except that: as shown in fig. 2, in the semi-dry sintering desulfurization ash oxidation apparatus of the present embodiment, a liquid pipe 330 is extended into a gas pipe 240, and an oxygen-aid solution in an oxygen-aid container 310 is introduced into the bottom of a reactor cavity 110 under the driving of a gas supply unit 200. The bottom of the liquid conduit 330 is provided with a bubble generator 242, the bubble generator 242 allowing for a uniform distribution of the gas and oxygen-assist solution in the reactor cavity 110. So that the oxygen-assisting agent solution is CaSO in the desulfurization ash in the process of combining the desulfurization ash 3 After the ion state is formed into the solution, the oxygen-containing gas can quickly react with the H in the solution state 2 SO 3 Bind and undergo oxidation to form SO 4 2- Thereby accelerating the reaction rate.
The acid auxiliary agent is dichloroacetic acid (CHCl) 2 COOH) pKa in water at 25 °c 1 1.30, the oxygen-assisting agent in the embodiment is dichloroacetic acid, and the dichloroacetic acid is mixed with water to obtain an oxygen-assisting agent solution. The oxygen-assisting agent greatly improves the oxidation efficiency of the desulfurization ash, and realizes the oxidation of the desulfurization ash under the condition of low temperature of the open container. And (3) obtaining reactant precipitate after the reaction is finished, namely the oxidized modified desulfurization ash, and heating and drying the obtained product at the temperature of 100 ℃ to obtain dry powder, wherein the content of calcium sulfate dihydrate in the dry powder is up to 96.1%.
Example 3
The basic content of this embodiment is the same as embodiment 1, except that: as shown in fig. 3, a gas cooling mechanism 212 is disposed on a pipeline between the gas supply bottle 210 and the gas control valve 220 in this embodiment, and the gas cooling mechanism 212 is used for cooling the gas in the pipeline, so that the gas blown into the desulfurization ash mixed solution is low-temperature gas, and the gas temperature is 0 ℃, thereby promoting the reaction through reducing the reaction temperature, improving the reaction interface in the oxidation process of calcium sulfite, and further greatly improving the reaction efficiency. The acid auxiliary agent of the embodiment consists of oxalic acid and dichloroacetic acid, the mass ratio of the oxalic acid to the dichloroacetic acid is 2:1, and the oxygen assisting agent of the embodiment consists of oxalic acid and dichloroacetic acid. The oxygen-assisting agent greatly improves the oxidation efficiency of the desulfurization ash, realizes the oxidation of the desulfurization ash under the condition of low temperature of an open container, obtains reactant sediment after the reaction is completed, namely oxidized modified desulfurization ash, and heats and dries the reactant sediment at the temperature of 100 ℃ to obtain dry powder, wherein the content of calcium sulfate dihydrate in the dry powder reaches 95.2 percent.
Example 4
The basic content of this embodiment is the same as embodiment 1, except that: the oxygen-assisting agent comprises an acid auxiliary agent and an additive; and the acidic auxiliary agent and the additive consist of the following components in parts by mass: 10 parts of an acid auxiliary agent and 8 parts of an additive, wherein the acid auxiliary agent in the embodiment is oxalic acid; the additive comprises citric acid triamine and pyruvic acid, and comprises the following components in parts by mass: 2-4 parts of citric acid triamine and pyruvic acid: 6-8 parts of a lubricant; this example preferably uses 2 parts of triamine citrate, pyruvic acid: 6 parts. The oxygen-assisting agent greatly improves the oxidation efficiency of the desulfurization ash, and realizes the oxidation of the desulfurization ash under the low-temperature condition of the open container.
The method for oxidizing the desulfurization ash by using the oxidation device comprises the following specific steps:
s1, removing impurities and drying
Mixing the desulfurized ash raw material with water, removing large-particle insoluble matters on a sieve through a 200-mesh water sieve, obtaining desulfurized ash after impurity removal through vacuum suction filtration, and then placing the desulfurized ash into a drying oven for drying for 4 hours at 105 ℃;
s2, preparing a desulfurization ash solution
Mixing 25g of the desulfurization ash obtained in the step S1 with deionized water, wherein the solid-to-liquid ratio of the desulfurization ash to the deionized water is 1/30, and placing the mixture into a gas bath vibration box to sufficiently vibrate for 30min at 50 ℃ to obtain a desulfurization ash mixed solution;
s3, desulphurized ash acid oxidation
(1) The mass ratio of the oxygen assisting agent to the filtered and decontaminated desulfurization ash is 0.2-0.3, and the mass ratio is 0.3 in the embodiment; dissolving 7.5g of an oxygen-assisting agent in deionized water to obtain an oxygen-assisting agent solution, wherein the mass ratio of the oxygen-assisting agent to the deionized water is 0.05-0.2, and the implementation is preferably 0.2 to obtain 45g of the oxygen-assisting agent solution; the specific preparation method of the oxygen assisting agent comprises the following steps: the acid aid is mixed with water and then the additive is added to the acid aid solution to obtain an oxygen aid solution, i.e., in this example, 4.17g of oxalic acid powder is mixed with 37.5g of water, then the additive is added to the acid aid solution to obtain an oxygen aid solution, and the oxygen aid solution is added to the oxygen aid container 310.
(2) Adding the desulfurized fly ash mixed solution into the inner cavity 110 of the reactor, controlling the constant temperature of the constant temperature outer cavity 120, controlling the temperature in the constant temperature outer cavity to be 0 ℃, opening a gas control valve 220 of the gas supply unit 200, and blowing oxygen-containing gas into the desulfurized fly ash mixed solution, wherein the oxygen-containing gas is oxygen-enriched air, and the oxygen volume ratio of the oxygen-enriched air is 40-60%, and the preferred oxygen volume ratio of the embodiment is 45%; at the same time, the flow control valve 320 of the oxygen-aid injection unit 300 is opened, the oxygen-aid solution is injected from the oxygen-aid container 310 to the bottom of the reactor cavity 110 through the liquid pipeline 330, and the oxygen-aid solution is uniformly injected to the bottom of the desulfurization ash mixed solution in the process of oxidizing the desulfurization ashThe reaction time is 100min; in the reaction process, the blowing flow of the oxygen-containing gas regulated and controlled by the gas control valve 220 and the flowmeter 230 is 12ml/min, the gas pipe outlet 241 of the gas pipeline 240 is arranged corresponding to the liquid outlet 331, and the gas pipe outlet 241 is sprayed towards the liquid outlet 331, so that the oxygen-assisting agent solution is CaSO in the desulfurization ash combination process 3 After the ion state is formed into the solution, the oxygen-containing gas can quickly react with the H in the solution state 2 SO 3 Bind and undergo oxidation to form SO 4 2- Thereby accelerating the reaction rate. Noteworthy are: the injection time of the oxygen-assisting agent solution is the same as the reaction time, namely, the oxygen-assisting agent solution is slowly and uniformly injected into the bottom of the desulfurization ash mixed solution from the beginning of the reaction to the end of the reaction, namely, 45g of the oxygen-assisting agent solution is slowly and uniformly injected in the reaction time of 100 min. The reactant precipitate is the oxidized and modified desulfurization ash after the reaction is finished, and the oxidized and modified desulfurization ash is heated and dried at the temperature of 100 ℃ to obtain dry powder, wherein the content of calcium sulfate dihydrate in the dry powder reaches 96.6 percent, and the oxidation efficiency of the desulfurization ash is greatly improved by adopting the oxygen promoter disclosed by the invention, and the oxidation of the desulfurization ash is realized under the condition of low temperature of an open container.
Example 5
The basic content of this embodiment is the same as embodiment 4, except that: the oxygen-assisting agent of the embodiment comprises an acidic auxiliary agent and an additive; and the acidic auxiliary agent and the additive consist of the following components in parts by mass: 15 parts of acid auxiliary agent and 10 parts of additive, wherein the additive comprises citric acid triamine, pyruvic acid and ethanol, and comprises the following components in parts by mass: 2 parts of citric acid triamine and pyruvic acid: 4 parts of ethanol: 4 parts. The oxygen-assisting agent greatly improves the oxidation efficiency of the desulfurization ash, realizes the oxidation of the desulfurization ash under the low-temperature condition of an open container, and ensures that the content of calcium sulfate dihydrate in the dry powder after oxidation reaches 95.8 percent, thereby greatly reducing the cost of the oxidation treatment of the desulfurization ash, and changing the reaction interface in the oxidation process of the calcium sulfite in the desulfurization ash under the ionic state due to the common use of the citric acid triamine, the acid auxiliary agent and the ethanol solution 3 2- At the same time also improves the H pair in the solution 2 SO 3 Solubility of (C) and thereby prolong H 2 SO 3 The residence time in the solution improves the oxidation efficiency of calcium sulfite in the desulfurized fly ash and avoids SO 2 Is not limited.
Example 6
The basic content of this embodiment is the same as embodiment 4, except that: the oxygen-assisting agent of the embodiment comprises an acidic auxiliary agent and an additive; and the acidic auxiliary agent and the additive consist of the following components in parts by mass: 15 parts of acid auxiliary agent and 10 parts of additive, wherein the additive comprises citric acid triamine, pyruvic acid, ethanol and CaCl 2 The coating comprises the following components in parts by mass: 2 parts of citric acid triamine and pyruvic acid: 3 parts of ethanol: 4 parts of CaCl 2 :1 part. The oxygen-assisting agent greatly improves the oxidation efficiency of the desulfurization ash, and realizes the oxidation of the desulfurization ash in an open container under the condition of low temperature, and the content of calcium sulfate dihydrate in the oxidized dry powder reaches 95.2 percent. CaCl (CaCl) 2 Provides sufficient Ca for calcium sulfate precipitation 2+ Thereby to promote, H 2 SO 3 The generation of precipitated substances after oxidation promotes the rapid progress of the reaction and increases H 2 SO 3 Is used for the utilization of the system.
Example 7
The basic content of this embodiment is the same as embodiment 4, except that: the oxygen-assisting agent of the embodiment comprises an acidic auxiliary agent and an additive; and the acidic auxiliary agent and the additive consist of the following components in parts by mass: 15 parts of acid auxiliary agent and 11 parts of additive, wherein the additive comprises citric acid triamine, pyruvic acid, ethanol and sodium ethylenediamine tetraacetate, and the additive comprises the following components in parts by mass: 2 parts of citric acid triamine and pyruvic acid: 4 parts of ethanol: 4 parts of sodium ethylenediamine tetraacetate: 1 part. It is worth noting that sodium ethylenediamine tetraacetate is insoluble in ethanol, so that the additive is difficult to mix sufficiently, and the specific preparation method of the oxygen promoter comprises the following steps: firstly, mixing an acid auxiliary agent with water, then adding the sodium ethylenediamine tetraacetate of the additive into the acid auxiliary agent solution, and finally, sequentially adding other components of the additive into the acid auxiliary agent solution to obtain the oxygen-assisting agent solution. The oxygen-assisting agent greatly improves the oxidation efficiency of the desulfurization ash, and realizes the oxidation of the desulfurization ash under the conditions of an open container and low temperature, and the content of calcium sulfate dihydrate in the oxidized dry powder reaches 96.7 percent.
Example 8
The basic content of this embodiment is the same as embodiment 1, except that: the oxygen-assisting agent of the embodiment comprises an acidic auxiliary agent and an additive; and the acidic auxiliary agent and the additive consist of the following components in parts by mass: 15 parts of acid auxiliary agent and 10 parts of additive, wherein the acid auxiliary agent is oxalic acid, and the additive comprises citric acid triamine, pyruvic acid, ethanol, diethyl ether and hydrogen peroxide, and comprises the following components in parts by mass: 1-2 parts of citric acid triamine; 3-4 parts of pyruvic acid; 3-4 parts of ethanol; 0.5-1 part of diethyl ether; 0.5-1 part of hydrogen peroxide; in the embodiment, 2 parts of triamine citrate, 3 parts of pyruvic acid, 4 parts of ethanol, 0.5 part of diethyl ether and 0.5 part of hydrogen peroxide are preferable.
The method for oxidizing the desulfurization ash by using the oxidation device comprises the following specific steps:
s1, removing impurities and drying
Mixing the desulfurized ash raw material with water, removing large-particle insoluble matters on a sieve through a 200-mesh water sieve, obtaining desulfurized ash after impurity removal through vacuum suction filtration, and then placing the desulfurized ash into a drying oven for drying for 4 hours at 105 ℃;
s2, preparing a desulfurization ash solution
Mixing 30g of the desulfurization ash obtained in the step S1 with deionized water, wherein the solid-to-liquid ratio of the desulfurization ash to the deionized water is 1/20, and placing the mixture into a gas bath vibration box to sufficiently vibrate for 30min at 50 ℃ to obtain a desulfurization ash mixed solution;
s3, desulphurized ash acid oxidation
(1) The mass ratio of the oxygen assisting agent to the filtered and decontaminated desulfurization ash is 0.2-0.3, and the mass ratio is 0.2 in the embodiment; dissolving 6g of an oxygen-assisting agent in deionized water to obtain an oxygen-assisting agent solution, wherein the mass ratio of the oxygen-assisting agent to the deionized water is 0.05-0.2, and the implementation is preferably 0.1 to obtain 66g of the oxygen-assisting agent solution; the specific preparation method of the oxygen assisting agent comprises the following steps: the acid aid is mixed with water and then the additive is added to the acid aid solution to obtain an oxygen aid solution, i.e., in this example, 3.6g of oxalic acid powder is mixed with 60g of water, 2.4g of the additive is added to the acid aid solution to obtain an oxygen aid solution, and the oxygen aid solution is added to the oxygen aid container 310.
(2) Adding the desulfurized fly ash mixed solution into the reactor inner cavity 110, controlling the constant temperature of the constant temperature outer cavity 120, keeping the temperature in the reactor at 10 ℃, and opening a gas control valve 220 of the gas supply unit 200 to blow oxygen-containing gas into the desulfurized fly ash mixed solution, wherein the oxygen-containing gas is oxygen-enriched air; simultaneously, a flow control valve 320 of the oxygen-aid injection unit 300 is opened, an oxygen-aid solution is injected into the bottom of the inner cavity 110 of the reactor from the oxygen-aid container 310 through a liquid pipeline 330, the oxygen-aid solution is uniformly injected into the bottom of the desulfurization ash mixed solution in the process of oxidizing the desulfurization ash, and the reaction time is 80min; in the reaction process, the blowing flow of the oxygen-containing gas regulated and controlled by the gas control valve 220 and the flowmeter 230 is 10ml/min, the gas pipe outlet 241 of the gas pipeline 240 is arranged corresponding to the liquid outlet 331, and the gas pipe outlet 241 is sprayed towards the liquid outlet 331, so that the oxygen-assisting agent solution is CaSO in the desulfurization ash combination process 3 After the ion state is formed into the solution, the oxygen-containing gas can quickly react with the H in the solution state 2 SO 3 Bind and undergo oxidation to form SO 4 2- Thereby accelerating the reaction rate. Noteworthy are: the injection time of the oxygen-assisting agent solution is the same as the reaction time, namely, the oxygen-assisting agent solution is slowly and uniformly injected into the bottom of the desulfurization ash mixed solution from the beginning of the reaction to the end of the reaction, namely, 14g of the oxygen-assisting agent solution is slowly and uniformly injected in the reaction time of 80 min. After the reaction is finished, reactant sediment is obtained, the sediment is heated and dried at the temperature of 100 ℃ to obtain dry powder, the content of calcium sulfate dihydrate in the dry powder reaches 97.3 percent, the oxidation efficiency of the desulfurization ash is greatly improved by adopting the oxygen promoter, and the oxidation of the desulfurization ash is realized under the condition of low temperature of an open container.
The reaction mechanism of the oxygen promoter for promoting the oxidation of the desulfurization ash after the oxygen promoter is added into the desulfurization ash mixed solution is probably as follows: oxalic acid in the oxygen-assisting agent is ionized to form H after being dissolved in water + The combined action of the citric acid triamine and oxalic acid promotesSO in sulfurous acid 3 2- Enters the solution, and at the same time, the addition of the ethanol solution improves the reaction of H in the solution 2 SO 3 And under the action of hydrogen peroxide and oxygen to promote H 2 SO 3 Oxidation to H 2 SO 4 Oxidizing the formed SO 4 2- Will be combined with Ca 2+ A precipitate was formed. After the diethyl ether of the oxygen assisting agent is added into the desulfurization ash mixed solution, the diethyl ether floats on the upper part of the solution due to SO 2 Dissolved in diethyl ether, thereby restricting SO 2 At the same time, the ethanol in the solution system can lead the sulfur dioxide dissolved in the diethyl ether to return to the solution system again to participate in oxidation reaction, and part of hydrogen peroxide dissolved in the ethanol can oxidize SO in the diethyl ether 2 Thereby improving SO 2 At the same time, limit SO 2 Escape.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will be understood that various modifications and changes may be made without departing from the scope of the invention as defined by the appended claims. The detailed description is to be regarded as illustrative in nature and not as restrictive, and if there are any such modifications and variations that fall within the scope of the invention described herein. Furthermore, the background art is intended to illustrate the status and meaning of the development of the technology and is not intended to limit the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined (e.g., between various embodiments), adapted, and/or substituted as would be recognized by those skilled in the art in light of the foregoing detailed description. The limitations in the claims are to be interpreted broadly based on the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. For example, in the present invention, the term "preferably" is not exclusive, and here it means "preferably, but not limited to". Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.

Claims (1)

1. A method for oxidizing desulfurization ash by an oxidation device, which is characterized in that: the method comprises the following specific steps:
s1, removing impurities and drying
Mixing the desulfurized ash raw material with water, removing large-particle insoluble substances through a water screen, and vacuum filtering to obtain desulfurized ash after impurity removal;
s2, preparing a desulfurization ash solution
Mixing the desulfurization ash obtained in the step S1 with deionized water, wherein the solid-to-liquid ratio of the desulfurization ash to the deionized water is 1/20-1/50, and sufficiently oscillating to obtain a desulfurization ash mixed solution;
s3, desulphurized ash acid oxidation
(1) The mass ratio of the oxygen-assisting agent to the filtered and decontaminated desulfurization ash is 0.2-0.3, the oxygen-assisting agent is dissolved in deionized water to obtain an oxygen-assisting agent solution, and then the oxygen-assisting agent solution is added into an oxygen-assisting agent container (310) of the desulfurization ash oxidation device;
the oxidation device comprises
A reaction unit (100), the reaction unit (100) comprising a reactor cavity (110), the reactor cavity (110) being for containing an oxidized desulfurization ash mixture;
the gas supply unit (200), the gas pipeline (240) of the gas supply unit (200) stretches into the bottom of the inner cavity (110) of the reactor, the gas supply unit (200) is used for blowing oxygen-containing gas into the desulfurized ash mixed liquor;
the oxygen-assisted agent injection unit (300), the oxygen-assisted agent injection unit (300) comprises an oxygen-assisted agent container (310) and a liquid pipeline (330), the oxygen-assisted agent container (310) is communicated with the liquid pipeline (330), and the oxygen-assisted agent injection unit (300) is used for injecting an oxygen-assisted agent solution into the desulfurization ash mixed solution;
the liquid pipeline (330) stretches into the bottom of the inner cavity (110) of the reactor, a liquid outlet (331) is formed in the bottom of the liquid pipeline (330), an air pipe outlet (241) of the gas pipeline (240) is arranged corresponding to the liquid outlet (331), and the air pipe outlet (241) sprays towards the liquid outlet (331);
the liquid pipeline (330) stretches into the gas pipeline (240), and the oxygen-assisting agent solution in the oxygen-assisting agent container (310) enters the bottom of the inner cavity (110) of the reactor under the driving of the gas supply unit (200);
the bottom of the liquid pipeline (330) is provided with a bubble generator (242), and the bubble generator (242) ensures that gas and oxygen-aid solution are uniformly distributed in the inner cavity (110) of the reactor;
a constant temperature outer cavity (120) is arranged outside the reactor inner cavity (110), and the constant temperature outer cavity (120) is used for keeping the reactor inner cavity (110) at a constant temperature;
the oxygen-assisting agent comprises an acidic auxiliary agent, wherein the pKa1 acidity coefficient of the acidic auxiliary agent is between that of sulfurous acid and sulfuric acid, and the oxygen-assisting agent is used for oxidizing calcium sulfite in desulfurization ash; the acid auxiliary agent is easy to dissolve in water, and the pKa1 acidity coefficient of the acid auxiliary agent in water at 25 ℃ is as follows: 1.00-1.89; the acid auxiliary agent is oxalic acid or dichloroacetic acid or a combination of the oxalic acid and dichloroacetic acid; the oxygen-assisting agent comprises the following components in parts by mass:
10-20 parts of an acidic auxiliary agent;
8-12 parts of additive;
wherein the additive comprises citric acid triamine and pyruvic acid;
(2) Adding the desulfurization ash mixed solution into an inner cavity (110) of a reactor, opening an inner cavity stirrer (111), blowing oxygen-containing gas into the desulfurization ash mixed solution, uniformly injecting an oxygen-aid solution in an oxygen-aid container (310) into the bottom of the desulfurization ash mixed solution in the process of oxidizing the desulfurization ash, and obtaining oxidized desulfurization ash; the time of the oxidation reaction of the desulfurization ash mixed solution is 80-150min, and the injection time of the oxygen-assisting agent solution is the same as the reaction time.
CN201710123582.6A 2017-03-03 2017-03-03 Device and method for oxidative modification of sintering semi-dry desulfurization ash Active CN107399753B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710123582.6A CN107399753B (en) 2017-03-03 2017-03-03 Device and method for oxidative modification of sintering semi-dry desulfurization ash

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710123582.6A CN107399753B (en) 2017-03-03 2017-03-03 Device and method for oxidative modification of sintering semi-dry desulfurization ash

Publications (2)

Publication Number Publication Date
CN107399753A CN107399753A (en) 2017-11-28
CN107399753B true CN107399753B (en) 2023-05-26

Family

ID=60404331

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710123582.6A Active CN107399753B (en) 2017-03-03 2017-03-03 Device and method for oxidative modification of sintering semi-dry desulfurization ash

Country Status (1)

Country Link
CN (1) CN107399753B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103551029A (en) * 2013-10-22 2014-02-05 重庆大学 Modification method for semi-dry sintering flue gas desulfurization ash
CN105819480A (en) * 2016-03-18 2016-08-03 株洲醴陵旗滨玻璃有限公司 Semi-dry process flue gas desulfurized ash modification treatment method
CN206553205U (en) * 2017-03-03 2017-10-13 安徽工业大学 One kind sintering semi-dry desulphurization ash oxidation unit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103551029A (en) * 2013-10-22 2014-02-05 重庆大学 Modification method for semi-dry sintering flue gas desulfurization ash
CN105819480A (en) * 2016-03-18 2016-08-03 株洲醴陵旗滨玻璃有限公司 Semi-dry process flue gas desulfurized ash modification treatment method
CN206553205U (en) * 2017-03-03 2017-10-13 安徽工业大学 One kind sintering semi-dry desulphurization ash oxidation unit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"添加剂促进亚硫酸钙氧化的实验研究";汪黎东等;《环境污染治理技术与设备》;20060430;第7卷(第4期);第41-45页 *

Also Published As

Publication number Publication date
CN107399753A (en) 2017-11-28

Similar Documents

Publication Publication Date Title
CN102602973B (en) Method for synthesizing ultrafine calcium carbonate by utilizing carbide slag
CN107400929B (en) A method of the sintering flue gas semi-dry desulphurization ash based on acid oxidation prepares calcium sulfate crystal whiskers
CN103551018B (en) A kind of sulfur-containing tail gas purifies and recoverying and utilizing method
CN104311865B (en) A kind of rubber surface method of modifying
CN102230088A (en) Method for extracting manganese from manganese-enriched slag
CN105692717B (en) A kind of bodied ferric sulfate and preparation method thereof
CN105110301A (en) Method for improving transparency of acid prepared from secondary baking flue gas of cyanidation tailings
CN109095578A (en) A kind of method of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium
CN103864154A (en) Production method of liquid polymeric ferric sulfate water purifying agent
CN103146920A (en) Pretreatment method for refractory gold ore containing arsenic and sulfur
CN107188292B (en) Method for purifying arsenic-containing waste liquid by utilizing cyaniding silver extraction waste residues
CN107399753B (en) Device and method for oxidative modification of sintering semi-dry desulfurization ash
CN107399752B (en) A kind of method of sintering flue gas semi-dry desulphurization ash acid oxidation modification
CN102286783B (en) New method for preparing calcium sulfate whiskers
CN113929328A (en) Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer
CN107399754B (en) A kind of pro-oxygenic agent for the oxidation of sintering flue gas semi-dry desulphurization ash
CN104294058B (en) A kind of processing method of high-sulfur high-arsenic carbon material gold mine
CN109081382A (en) A kind of processing technology of bodied ferric sulfate
CN107760867A (en) The method for preparing mixed rare earth carbonate with mixed precipitant under sulfuric acid system
CN109517973A (en) A kind of method of vanadium-containing shale biology-baking acid immersion joint Vanadium Concentrationin
CN112830505B (en) Method for purifying salt mother liquor slurry by flue gas method
CN206553205U (en) One kind sintering semi-dry desulphurization ash oxidation unit
CN103880651B (en) Reaction of high order prepares method and the device of oxoethanoic acid
CN209721679U (en) A kind of sodium citrate parses the device of lean solution purification and its by-product gypsum whisker
CN1114011C (en) Alkaline pulping process of wheel straw without drainage of black liquid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant