CN102432211A - Method for preparing desulfurized gypsum - Google Patents
Method for preparing desulfurized gypsum Download PDFInfo
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- CN102432211A CN102432211A CN2011104412825A CN201110441282A CN102432211A CN 102432211 A CN102432211 A CN 102432211A CN 2011104412825 A CN2011104412825 A CN 2011104412825A CN 201110441282 A CN201110441282 A CN 201110441282A CN 102432211 A CN102432211 A CN 102432211A
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Abstract
The invention discloses a method for preparing desulfurized gypsum, belonging to the technical field of flue gas desulfurization. The method comprises the following steps: taking desulfurizing slurry generated by flue gas wet desulfurization, adding a crystal grain increase agent into the desulfurizing slurry to carry out oxidization, separating out impurities, and dehydrating to obtain the desulfurized gypsum, wherein the crystal grain increase agent is at least one of surfactant, flocculant and inorganic salts. The method disclosed by the invention can greatly lower the water content of the desulfurized gypsum and enhance the purity of the desulfurized gypsum, thereby enhancing the quality of the desulfurized gypsum.
Description
Technical field
The present invention relates to the flue gas desulfurization technique field, be specifically related to a kind of method for preparing desulfurated plaster.
Background technology
Wet desulfurizing process be use the most extensively at present, the most sophisticated flue gas desulfurization technique of technology, account for 90% of flue gas desulfurization (FGD) fired power generating unit capacity be installed.Wet desulfurizing process comprises alkaline waste sulfur removal technologies such as limestone-gypsum method, white clay, acetylene sludge-gypsum process, and its desulfurizing byproduct is a desulfurated plaster.The desulfurated plaster staple is a terra alba, can be widely used in preparing building productses such as cement, plasterboard, gypsum block.In general need the gypsum of desulphurization system output to satisfy water ratio＜10% the desulfurated plaster recycling, purity conditions such as (in terra alba massfractions in the butt)＞90%.Yet desulfurated plaster often＞10% often is difficult to reach These parameters, particularly water ratio at present, has restricted the recycling of desulfurated plaster to a certain extent.
Except that desulphurization system conventional index (like pH value etc.), the factor that influences desulfurated plaster water ratio and purity is mainly following:
1, gypsum slurries Central Asia calcium sulphate content, calcium sulfite will reduce the dewatering of desulfurated plaster in the desulfurated plaster, reduce desulfurated plaster purity simultaneously, calcium sulfite content mainly be since the desulfurization slurry oxidation insufficient due to.
2, foreign matter content in the gypsum slurries mainly contains the impurity that flying dust and sweetening agent are brought into, the technology that particularly adopts trade refuses such as carbide slag, white clay to carry out desulfurization, and foreign matter content is higher relatively.These impurity can influence the crystallization of gypsum on the one hand and grow up, and cause desulfurated plaster crystal grain tiny, are unfavorable for gypsum dehydration; On the other hand, these impurity often density are lower, and viscosity is bigger, and when gypsum slurries flows to when carrying out suction filtration on the band filter filter cloth, impurity forms the coverture of one deck brown on its top layer, influence vacuum filtration; Simultaneously, partial impurities is mixed in the gypsum intergranule, has stopped up the passage of free-water between gypsum crystal, makes the gypsum dehydration difficulty; In addition, foreign matter content is higher will reduce desulfurated plaster purity.
3, send into the gypsum slurries solid content of dehydration equipment, if the gypsum slurries solid content is too low, and then slurries are moisture higher relatively, will increase the dehydration equipment load, causes the gypsum filter cake water ratio higher.
In conventional sulfur removal technology, desulfurization slurry is squeezed into hydrocyclone by slush pump and is carried densely after oxidation is accomplished on the absorption tower, and underflow is sent into dehydration equipment such as vacuum band filter and dewatered, and impurity is mainly through system's discharge of wastewater in the desulphurization system.Its unfavorable factor to desulfurated plaster water ratio and purity mainly contains:
1, desulfurization slurry is accomplished oxidation in the absorption tower; The regulation and control of parameters such as pH are restricted by the sulfurous gas absorption process, and secondly, the slurries residence time receives the absorption tower capacity limitation; Grain formation and the time of growing up is relatively limited; Simultaneously, because slurries repeatedly through recycle pump and spraying layer reflux cycle, are unfavorable for the gypsum grain growth.
2, only adopt the waste water system waste discharge to reduce impurity; The waste water that effluxes is hydrocyclone top stream; Because hydrocyclone is limited to the separate impurities effect, impurity concentration is lower and have higher relatively gypsum content in the efflux wastewater, therefore; The Waste Water Treatment load is bigger, and the Impurity removal amount is also relatively limited.
Summary of the invention
The invention provides a kind of method for preparing desulfurated plaster, reduce the water ratio of desulfurated plaster, improve the purity of desulfurated plaster.
A kind of method for preparing desulfurated plaster; Comprise: get the desulfurization slurry that smoke-gas wet desulfurization produces; Add crystal grain in the desulfurization slurry and increase and carry out oxidation, separating impurity, dehydration after the agent and make desulfurated plaster, it is at least a in tensio-active agent, flocculation agent and the inorganic salt that described crystal grain increases agent.
The formation of nucleus is the crystalline the first step in the gypsum crystallization process, and according to calculation of thermodynamics, must grow up to greater than the critical size of nucleation the time could stable existence and be unlikely and die away for the initial plumule that forms in the system.The free energy reduction value that general plumule forms must reach 1/3 of this nucleating surface ability, just can cross the surface energy energy barrier, forms stable nucleus.
Described tensio-active agent is X 2073, sodium lauryl sulphate or sodium laurate.Tensio-active agent can change the surface free energy of solution, and can optionally be adsorbed on the thermodynamic property that changes solid surface on the solid surface, thereby reaches the effect that promotes grain growing.
Described flocculation agent is an activated silica.Activated silica can change the surface free energy of solution, and can optionally be adsorbed on the thermodynamic property that changes solid surface on the solid surface, thereby reaches the effect that promotes grain growing.
Described inorganic salt are vitriol.Improve sulfate ion concentration in the desulfurization slurry promoting grain growing through adding vitriol, the increase of gypsum crystal grain can significantly increase the dewatering of gypsum, reduces the water ratio of gypsum behind suction filtration.
The addition that described crystal grain increases agent is 0.01-1g/L.Addition is too low, and DeGrain, addition are too high, bubbles easily, and brings more impurity (additive itself is an impurity as far as gypsum) into, influences gypsum quality (purity and harmful ion content), and the too high Financial cost of addition is just high simultaneously.
Comprise: flue gas is fed carry out wet desulphurization in the absorption tower; The desulfurization slurry that produces is sent into oxidation tank; Add crystal grain and increase and carry out oxidation, separating impurity, dehydration after the agent and make desulfurated plaster, it is at least a in tensio-active agent, flocculation agent and the inorganic salt that described crystal grain increases agent.Desulfurization slurry in the absorption tower is exported to oxidation in the tower external oxidation jar; Adopt tower external oxidation technology; Parameters such as pH value can independently be regulated and control, and can carry out the required optimum parameter regulation and control of oxidation, and oxidation is more thorough; Contain especially the sweetening agent of reducing substances, can overcome the influence of reducing impurity calcium sulfite oxidation for carbide slag etc.; Avoided recycle pump and sprinkling system crushing effect, be beneficial to grain growth gypsum crystal grain.
The device of described separating impurity is the separating tank of built-in whisking appliance.Separating tank separates the tiny sticky contaminant in upper strata, and impurity separates more thorough, has avoided the influence of impurity to gypsum dehydration, has improved desulfurated plaster purity simultaneously; Middle part density less relatively slurries return the absorption tower, have realized that the separating tank slurries carry densely, have saved conventional gypsum swirler-concentration unit, have practiced thrift investment and energy consumption; Can be 1.1-1.4g/ml through regulating agitator speed control bottom serum density, generally speaking, 1.1-1.4g/ml helps being with filter to gypsum dehydration, and general vertical type agitator speed can be realized above-mentioned effect at 40-80r/min.
Beneficial effect of the present invention:
In desulfurization slurry, add crystal grain and increase after the agent, can increase desulfurated plaster crystal grain, increase the dewatering of gypsum slurries carrying out oxidation; Tower external oxidation technology can prolong the gypsum grain growth time, avoids recycle pump and the sprinkling system crushing effect to gypsum crystal grain; Separating tank separates more thorough, has avoided the influence of impurity to gypsum dehydration, has improved the purity of desulfurated plaster simultaneously.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
As shown in Figure 1, technical process of the present invention is:
Desulfurization slurry is sent into the desulfurization slurry in the absorption tower of desulfurization method of limestone-gypsum system 6 in the oxidation tank 1 for the desulfurization slurry that the desulfurization method of limestone-gypsum system produces, and adds crystal grain in the desulfurization slurry in oxidation tank 1 and increases agent 5; In oxidation tank 1, feed oxidation air 7 then; Slurries after the oxidation are thrown in the separating tank 2 through slush pump, in separating tank 2, inject service water 8, the slurries after the dilution oxidation then; Oxidation slurries after the dilution pass through the stirring layering of whisking appliance 4 in separating tank 2; Agitator speed is 40-80r/min, and upper solution 9 is to Sewage treatment systems, and density less relatively slurries 10 in middle part return the absorption tower; The bottom slurries are squeezed into dehydration equipment 3 through slush pump and are carried out gypsum dehydration, and dehydration equipment is selected vacuum band filter.
GBT5484-2000 is all adopted in the detection of desulfurated plaster filter cake moisture content and gypsum purity in following examples.
Adopt technology as shown in Figure 1, desulphurization system is the desulfurization method of limestone-gypsum system, adds X 2073 in the desulfurization slurry; X 2073 concentration is 0.03g/L in the interpolation rear slurry; Agitator speed is 50r/min, and separating tank bottom serum density is 1.21g/ml, adopts vacuum band filter to carry out suction filtration; The desulfurated plaster filter cake moisture content that obtains is 10.8%, and gypsum purity is 94%.
Adopt technology as shown in Figure 1, desulphurization system is the desulfurization method of limestone-gypsum system, adds X 2073 in the desulfurization slurry; X 2073 concentration is 0.05g/L in the interpolation rear slurry; Agitator speed is 70r/min, and separating tank bottom serum density is 1.15g/ml, adopts vacuum band filter to carry out suction filtration; The desulfurated plaster filter cake moisture content that obtains is 10.4%, and gypsum purity is 96%.
Adopt technology as shown in Figure 1, desulphurization system is the acetylene sludge-gypsum process desulphurization system, adds sodium lauryl sulphate in the desulfurization slurry; Sodium lauryl sulphate concentration is 0.03g/L in the interpolation rear slurry; Agitator speed is 40r/min, and separating tank bottom gypsum slurries density is 1.24g/ml, adopts vacuum band filter to carry out suction filtration; The desulfurated plaster filter cake moisture content that obtains is 9.8%, and gypsum purity is 97%.
Embodiment 4
Adopt technology as shown in Figure 1, desulphurization system is the acetylene sludge-gypsum process desulphurization system, adds sodium laurate in the desulfurization slurry; Sodium laurate concentration is 0.03g/L in the interpolation rear slurry; Agitator speed is 40r/min, and separating tank bottom gypsum slurries density is 1.24g/ml, adopts vacuum band filter to carry out suction filtration; The desulfurated plaster filter cake moisture content that obtains is 9.8%, and gypsum purity is 97%.
Adopt technology as shown in Figure 1, desulphurization system is the acetylene sludge-gypsum process desulphurization system, adds activated silica in the desulfurization slurry; Activated silica concentration is 0.5g/L in the interpolation rear slurry; Agitator speed is 80r/min, and separating tank bottom gypsum slurries density is 1.19g/ml, adopts vacuum band filter to carry out suction filtration; The desulfurated plaster filter cake moisture content that obtains is 10.8%, and gypsum purity is 92%.
Embodiment 6
Adopt technology as shown in Figure 1, desulphurization system is the acetylene sludge-gypsum process desulphurization system, adds sodium sulfate in the desulfurization slurry; Sodium sulfate concentration is 0.2g/L in the interpolation rear slurry; Agitator speed is 50r/min, and separating tank bottom gypsum slurries density is 1.20g/ml, adopts vacuum band filter to carry out suction filtration; The desulfurated plaster filter cake moisture content that obtains is 10.5%, and gypsum purity is 94%.
Claims (7)
1. method for preparing desulfurated plaster; Comprise: get the desulfurization slurry that smoke-gas wet desulfurization produces; Add crystal grain in the desulfurization slurry and increase and carry out oxidation, separating impurity, dehydration after the agent and make desulfurated plaster, it is at least a in tensio-active agent, flocculation agent and the inorganic salt that described crystal grain increases agent.
2. method according to claim 1 is characterized in that, described tensio-active agent is X 2073, sodium lauryl sulphate or sodium laurate.
3. method according to claim 1 is characterized in that, described flocculation agent is an activated silica.
4. method according to claim 1 is characterized in that, described inorganic salt are vitriol.
5. method according to claim 1 is characterized in that, the addition that described crystal grain increases agent is 0.01-1g/L.
6. method according to claim 1; It is characterized in that; Comprise: flue gas is fed carry out wet desulphurization in the absorption tower; The desulfurization slurry that produces is sent into oxidation tank, add crystal grain and increase and carry out oxidation, separating impurity, dehydration after the agent and make desulfurated plaster, it is at least a in tensio-active agent, flocculation agent and the inorganic salt that described crystal grain increases agent.
7. method according to claim 6 is characterized in that, the device of described separating impurity is the separating tank of built-in whisking appliance.
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| CN2011104412825A CN102432211A (en) | 2011-12-26 | 2011-12-26 | Method for preparing desulfurized gypsum |
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| CN2011104412825A CN102432211A (en) | 2011-12-26 | 2011-12-26 | Method for preparing desulfurized gypsum |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314905A (en) * | 2014-07-21 | 2016-02-10 | 上海境闲机械设备制造有限公司 | Dewatering technology for desulfurized gypsum |
| CN106186031A (en) * | 2016-07-12 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of desulfurated plaster preparation method changing alkali based on farmland |
| CN106187484A (en) * | 2016-07-11 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of desulfurated plaster improveing Wheat Growing Soils and production technology thereof |
| CN110898468A (en) * | 2019-11-27 | 2020-03-24 | 宜宾天原集团股份有限公司 | Method for improving filter pressing efficiency of desulfurized gypsum |
| CN112520823A (en) * | 2020-11-10 | 2021-03-19 | 河北国华定州发电有限责任公司 | Method for adding composite gypsum crystallization accelerator for improving crystallization quality of desulfurization slurry |
| CN113929328A (en) * | 2021-11-15 | 2022-01-14 | 华能沁北发电有限责任公司 | Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513766A (en) * | 2003-06-06 | 2004-07-21 | 浙江大学 | Techlogogy for making alpha semi-water desulfur gypsum using normal pressure salt solution method |
-
2011
- 2011-12-26 CN CN2011104412825A patent/CN102432211A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513766A (en) * | 2003-06-06 | 2004-07-21 | 浙江大学 | Techlogogy for making alpha semi-water desulfur gypsum using normal pressure salt solution method |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314905A (en) * | 2014-07-21 | 2016-02-10 | 上海境闲机械设备制造有限公司 | Dewatering technology for desulfurized gypsum |
| CN105314905B (en) * | 2014-07-21 | 2020-05-12 | 上海国惠环保科技集团有限公司 | Desulfurization gypsum dehydration process |
| CN106187484A (en) * | 2016-07-11 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of desulfurated plaster improveing Wheat Growing Soils and production technology thereof |
| CN106186031A (en) * | 2016-07-12 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of desulfurated plaster preparation method changing alkali based on farmland |
| CN110898468A (en) * | 2019-11-27 | 2020-03-24 | 宜宾天原集团股份有限公司 | Method for improving filter pressing efficiency of desulfurized gypsum |
| CN112520823A (en) * | 2020-11-10 | 2021-03-19 | 河北国华定州发电有限责任公司 | Method for adding composite gypsum crystallization accelerator for improving crystallization quality of desulfurization slurry |
| CN112520823B (en) * | 2020-11-10 | 2022-10-11 | 河北国华定州发电有限责任公司 | Method for adding composite gypsum crystallization accelerator for improving crystallization quality of desulfurization slurry |
| CN113929328A (en) * | 2021-11-15 | 2022-01-14 | 华能沁北发电有限责任公司 | Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer |
| CN113929328B (en) * | 2021-11-15 | 2023-03-03 | 华能沁北发电有限责任公司 | Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer |
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Application publication date: 20120502 |