CN101816890B - Carbide slag pretreatment process used in wet desulphurization - Google Patents
Carbide slag pretreatment process used in wet desulphurization Download PDFInfo
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- CN101816890B CN101816890B CN2009101557416A CN200910155741A CN101816890B CN 101816890 B CN101816890 B CN 101816890B CN 2009101557416 A CN2009101557416 A CN 2009101557416A CN 200910155741 A CN200910155741 A CN 200910155741A CN 101816890 B CN101816890 B CN 101816890B
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Abstract
The invention discloses a carbide slag pretreatment process used in wet desulphurization, which comprises the following steps of: performing ball milling on carbide slag slurry, adjusting the concentration of the carbide slag slurry, and then using the carbide slag slurry as a desulfurizing agent to perform the wet desulphurization on an exhaust gas, wherein an oxidant is added into the carbide slag slurry in the process of performing the ball milling on the carbide slag slurry or adjusting the concentration of the carbide slag slurry, and the oxidant is one or more of hypochlorite, chlorate and perchlorate. The carbide slag pretreatment process performs an oxidation pretreatment on the carbide slag slurry, and saves the investment cost caused by an overlarge volume of an absorption tower (for oxidation in the tower) or an oxidation tower (for oxidation outside the tower) because the oxidation time of calcium sulfite is too long. A catalyst entering the absorption tower along with the carbide slag slurry can simultaneously promote the oxidation rate of the calcium sulfite and calcium bisulfite in the oxidation tower, shorten the oxidation time, reduce the calcium bisulfite content in the slurry, and improve the quality of gypsum.
Description
Technical field
The invention belongs to the air pollution control technique field, relate to a kind of pretreating process of carbide slag slurry in wet method carbide slag/desulfurization of gypsum technology.
Background technology
Flue gas desulfurization is the sulfur method of unique large-scale commercial applications application of carrying out in the world, is control acid rain and SO
2The effective technical means of polluting the most.Wet type limestone/gypsum method has become the main flow of current flue gas desulfurization technique.In wet desulfurizing process, after the slurries absorbing sulfur dioxide, be that the neutralization reaction through lime stone, the oxidation reaction of sulphite obtain regenerating, the end product of desulfurization is a dihydrate gypsum.But limestone/gypsum method investment is higher with operating cost, takes up an area of greatlyyer, consumes limestone mineral resource simultaneously, the destruction environment
Because the generated by polyvinyl chloride by calcium carbide production technology is day by day ripe, the production of China's polyvinyl chloride is main with carbide mainly.And one ton of calcium carbide of every consumption will produce the 1.2-1.45t carbide slag, and according to statistics, annual carbide slag discharge capacity has reached ten million ton, and whole nation accumulative total heaped measure has exceeded hundred million tons.The main component of carbide slag is a calcium hydroxide, and is water-soluble, and long-term air storage meeting contaminated soil and phreatic water make the soil salinization and salinization of soil, and the stacking of a large amount of carbide slags also ties up valuable land resource.Therefore how recycling carbide slag, is the emphasis difficult problem of a lot of enterprises pay attention.Because the composition of carbide slag and desulfurizing agent lime, lime stone is very similar,, thereby realize the treatment of wastes with processes of wastes against one another, the realization changing waste into resources of turning waste into wealth so carbide slag also is used as the absorbent of flue gas desulfurization.It is ripe that the wet method carbide slag of replacing carbide slag with lime stone/gypsum method sulfur removal technology also obtains practice through actual items.Compare with lime, lime stone, carbide slag contains more reducing substances, like CaC
2, S
2-Deng, in the carbide slag slurry most of reducing substances in desulphurization system under about 6.0 the pH value condition its oxidation rate very slow, and calcium sulfite is the CaC in carbide slag slurry in the process that air blast starts oxidation
2, S
2-Just begin Deng after the reducing substances oxidation fully, the oxidization time that has prolonged slurries and slurries need the tower still of the bigger volume of design to satisfy the process conditions needs in the time of staying of tower still, increase invest, operating cost.The preliminary treatment of carbide slag becomes one of the key that carbide slag/gypsum method sulfur removal technology optimizes.
Summary of the invention
The present invention provides a kind of carbide slag pretreatment process that is used for wet desulphurization, in carbide slag, adds oxidant, and reducing substances causes the long problem of desulfurizing agent oxidization time in the carbide slag to solve.
A kind of carbide slag pretreatment process that is used for wet desulphurization; Handle as desulfurizing agent flue gas being carried out wet desulphurization after carbide slag slurry ball milling, the modulation concentration; In carbide slag slurry ball milling and/or modulation concentration process, add oxidant, described oxidant is one or more in hypochlorite, chlorate, the perchlorate.Oxidant relatively more commonly used has: NaClO
3, Mg (ClO
3)
2, HClO
4, Ca (ClO)
2, NaClO etc.
Because the reducing substances major part is with CaC in the carbide slag
2, S
2-Exist etc. situation, and can oxidation under high pH value.Utilize this characteristic in the ball milling of carbide slag pretreatment process and/or carbide slag slurry concentration process for preparation, to add proper amount of oxidant, with the reducing substances oxidation in the carbide slag.The absorption tower (oxidation in the tower) or the excessive cost of investment that produces of oxidizing tower (tower external oxidation) volume that cause the calcium sulfite oxidation hysteresis to produce because of reducing substances in the carbide slag have been saved.
The addition of described oxidant according to the content of reducing substances in the carbide slag, reasonably adds according to the stoichiometric relationship of reducing substances and oxidant reaction.With the calcium hypochlorite is example, and reducing substances is with S in the carbide slag
2-Calculate calcium hypochlorite and S
2-The mol ratio of reaction is 1: 1, then adds calcium hypochlorite according to this ratio.
Described oxidant is superior to adding in the process of carbide slag slurry modulation concentration most; Carbide slag during modulation concentration has passed through ball milling; Carbide slag is smaller through particle behind the ball milling; Be wrapped in the abundant stripping of reducing substances in the carbide slag, adding oxidant in this link of modulation concentration can be fast fully with the reducing substances oxidation.
Technology of the present invention is carried out oxidation pre-treatment to carbide slag slurry, has saved absorption tower (oxidation in the tower) or the excessive cost of investment that produces of oxidizing tower (tower external oxidation) volume because of the long generation of oxidization time of calcium sulfite.Oxidation rate with calcium sulfite and calcium bisulfite in the catalyst ability while catalytic oxidation tower on carbide slag slurry entering absorption tower shortens oxidization time, reduces the content of the calcium sulfite in the slurries, raising gypsum quality.
Description of drawings
Fig. 1 is the change slurry system schematic in the carbide slag/gypsum method sulfur removal technology that utilizes pretreating process of the present invention.
The specific embodiment
As shown in Figure 1; Carbide slag water in the usefulnessization pulp-water storage tank 7 in changing slag bath 1 is made into slurries and screens; Enter after pond 2 proportionings become the concentration of ball milling requirement in the middle of the slurries by changing stock pump, pump into ball mill 3 through the slurries line pump, the carbide slag slurry that mill is good is made into the required carbide slag slurry concentration of desulphurization system in carbide slag slurry concentration preparation pond 4; Add the oxidant that is stored in right amount in the oxidant storage tank 5 simultaneously at carbide slag slurry concentration process for preparation, the reducing substances in the oxidation carbide slag.The carbide slag slurry that in carbide slag slurry concentration preparation pond 4, stirs stop about 5 minutes pumps into finished product serum pot 6 through the finished product slush pump and stores.
Following examples are carried out according to above-mentioned pretreating process flow process shown in Figure 1.
Embodiment 1
Certain 130t/h of steam power plant coal furnace adopts carbide slag/gypsum wet sulfur removal technology desulfurization, exhaust gas volumn 140000m
3/ h, absorption tower import sulfur dioxide concentration 2200mg/Nm
3, add 2.3% calcium hypochlorite (the 2.3%th, the weight ratio of calcium hypochlorite and carbide slag) in carbide slag slurry concentration proportioning pond.Sulfurous acid is lower than 10mmol/L with concentration in the absorption tower, and chloride ion content is lower than 5000ppm.Gypsum purity is higher than 96.5%, calcium hydroxide residual volume 0.001%.
Embodiment 2
Certain chemical plant 220t/h coal furnace adopts carbide slag/gypsum wet sulfur removal technology, exhaust gas volumn 210000m
3/ h, absorption tower import SO 2 from fume concentration 3100mg/Nm
3, adding 3.5% hypochlorous acid (the 3.5%th, the weight ratio of hypochlorous acid and carbide slag) in carbide slag slurry concentration proportioning pond, sulfurous acid is lower than 9mmol/L with concentration in the absorption tower, and chloride ion content is lower than 3000ppm.Gypsum purity is higher than 97.2%, calcium hydroxide residual volume 0.001%.
Embodiment 3
Certain the 2 * 135MW/h of steam power plant unit coal-burning stove adopts carbide slag/gypsum wet sulfur removal technology, exhaust gas volumn 1200000m
3/ h, absorption tower import SO 2 from fume concentration is 1700mg/Nm
3, add 1.2% postassium hypochlorite (the 1.2%th, the weight ratio of postassium hypochlorite and carbide slag) in carbide slag slurry concentration proportioning pond.Sulfurous acid is lower than 8mmol/L with concentration in the absorption tower, and chloride ion content is lower than 1000ppm.The gypsum moisture content is lower than 9%, and purity is greater than 96.9%, and the calcium hydroxide residual volume is 0.0005%.
Embodiment 4
Certain 410t/h of steam power plant coal-burning boiler adopts carbide slag/gypsum wet flue gas desulfurizing technology, exhaust gas volumn 580000m
3/ h, absorption tower import SO 2 from fume concentration is 3300mg/Nm
3, adding 4% potassium chlorate (the 4%th, the weight ratio of potassium chlorate and carbide slag) in carbide slag slurry concentration proportioning pond, sulfurous acid is lower than 10mmol/L with concentration in the absorption tower, and chloride ion content is lower than 5000ppm.Gypsum purity is greater than 98.0%, and the calcium hydroxide residual volume is 0.001%.
Claims (3)
1. carbide slag pretreatment process that is used for wet desulphurization; Handle as desulfurizing agent flue gas being carried out wet desulphurization after carbide slag slurry ball milling, the modulation concentration; It is characterized in that: in carbide slag slurry ball milling and/or modulation concentration process, add oxidant, described oxidant is one or more in hypochlorite, chlorate, the perchlorate.
2. carbide slag pretreatment process as claimed in claim 1 is characterized in that: described oxidant is NaClO
3, Mg (ClO
3)
2, Ca (ClO)
2, among the NaClO one or more.
3. carbide slag pretreatment process as claimed in claim 1 is characterized in that: described oxidant adds in the process of carbide slag slurry modulation concentration.
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| CN101816890B true CN101816890B (en) | 2012-06-27 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091525B (en) * | 2010-12-23 | 2012-11-21 | 浙江天蓝环保技术股份有限公司 | Device and process for preparing carbide slag desulfurization seriflux from recovered ferroselenium |
| CN105107367B (en) * | 2015-09-16 | 2017-12-22 | 石河子开发区莱蒙钙业有限公司 | It is a kind of to use the method that carbide slag is raw material production desulfurizing agent |
| CN112090250B (en) * | 2020-08-13 | 2022-12-30 | 中冶华天工程技术有限公司 | On-line slow-release oxidation type flue gas circulating fluidized bed desulfurization method and system |
| CN112691535A (en) * | 2020-12-16 | 2021-04-23 | 湖北工业大学 | Carbide slag-based sulfur dioxide curing agent and preparation method thereof |
| CN114772625A (en) * | 2022-04-12 | 2022-07-22 | 四川大学 | Method for dissolving out calcium ions in carbide slag and method for mineralizing and storing CO by using calcium ions in carbide slag2Application of co-produced light calcium carbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168117A (en) * | 2007-08-30 | 2008-04-30 | 宁夏英力特电力集团股份有限公司 | Method for preparing high-performance solid desulfurizing agent by carbide slag slurry |
| CN101229473A (en) * | 2007-10-31 | 2008-07-30 | 浙江天蓝脱硫除尘有限公司 | Out tower oxidizing lime/acetylene sludge-gypsum process desulphurization technology and equipment |
| CN101318100A (en) * | 2008-07-21 | 2008-12-10 | 北京博奇电力科技有限公司 | Wet process of FGD with acetylene sludge as absorbing agent |
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2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168117A (en) * | 2007-08-30 | 2008-04-30 | 宁夏英力特电力集团股份有限公司 | Method for preparing high-performance solid desulfurizing agent by carbide slag slurry |
| CN101229473A (en) * | 2007-10-31 | 2008-07-30 | 浙江天蓝脱硫除尘有限公司 | Out tower oxidizing lime/acetylene sludge-gypsum process desulphurization technology and equipment |
| CN101318100A (en) * | 2008-07-21 | 2008-12-10 | 北京博奇电力科技有限公司 | Wet process of FGD with acetylene sludge as absorbing agent |
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Effective date of registration: 20110222 Address after: Hangzhou City, Zhejiang province Xiaoshan District 311202 North Street Xingyi Village Applicant after: Zhejiang Tianlan Environmental Protection Technology Co., Ltd. Address before: Hangzhou City, Zhejiang province Xiaoshan District 311202 North Street Xingyi Village Applicant before: Zhejiang Tianlan Environmental Protection Technology Co., Ltd. Co-applicant before: Wu Zhongbiao |
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