CN115400577A - Desulfurization method for mixed pulping of steel slag, clay and limestone and mixed desulfurizer - Google Patents
Desulfurization method for mixed pulping of steel slag, clay and limestone and mixed desulfurizer Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 103
- 230000023556 desulfurization Effects 0.000 title claims abstract description 103
- 239000002893 slag Substances 0.000 title claims abstract description 69
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 68
- 239000010959 steel Substances 0.000 title claims abstract description 68
- 239000004927 clay Substances 0.000 title claims abstract description 57
- 235000019738 Limestone Nutrition 0.000 title claims abstract description 48
- 239000006028 limestone Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004537 pulping Methods 0.000 title claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003546 flue gas Substances 0.000 claims abstract description 73
- 239000002699 waste material Substances 0.000 claims abstract description 61
- 239000011593 sulfur Substances 0.000 claims abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000004566 building material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 239000002002 slurry Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000003009 desulfurizing effect Effects 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 9
- 229960000892 attapulgite Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052625 palygorskite Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000011449 brick Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910001341 Crude steel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 buildings Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- WETINTNJFLGREW-UHFFFAOYSA-N calcium;iron;tetrahydrate Chemical compound O.O.O.O.[Ca].[Fe].[Fe] WETINTNJFLGREW-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The application discloses a desulfurization method for mixed pulping of steel slag, clay and limestone and a mixed desulfurizer. The mixed desulfurizer comprises waste steel slag particles, clay particles and limestone particles which are uniformly mixed. According to the application, the waste steel slag mixed clay, limestone and the like are adopted to prepare the mixed desulfurizer, so that the raw material source is wide, the cost is low, the waste steel slag can be effectively utilized, the components such as sulfur dioxide in sulfur-containing flue gas can be removed by the mixed desulfurizer at high efficiency and low cost, and the purpose of treating waste with waste is achieved; meanwhile, the by-product of the mixed desulfurizer after desulfurization of sulfur-containing flue gas has the advantages of small particles, convenience in processing and the like, can be used as a raw material in cement plants and building industries, does not generate secondary pollution, and the prepared building material also has the advantages of high strength, low cost and the like, so that comprehensive utilization of resources is realized.
Description
Technical Field
The application relates to a flue gas desulfurization method, in particular to a desulfurization method for mixing steel slag, clay and limestone to prepare slurry and a mixed desulfurizer, and belongs to the technical field of environmental protection.
Background
In 2020, the yield of crude steel in China exceeds 10 hundred million tons, and the correspondingly produced steel slag accounts for 10 to 15 percent of the yield of the crude steel, namely the yield of the steel slag exceeds 1 hundred million tons. However, the comprehensive utilization rate of the steel slag is not high at present, only about 30%, so that a large amount of steel slag is generated and cannot be utilized every year, a large amount of land area is occupied by piling up the steel slag year by year, and more serious, the environmental pollution is caused. At present, an effective way for utilizing large total amount and high added value of steel slag is to produce steel slag powder which is applied to building materials, buildings, concrete, roads and the like, but the current technology for producing the steel slag powder by using the steel slag has the outstanding problems of difficult grinding, high power consumption, low early strength of the produced steel slag powder and the like in the production process, and the large-scale production and engineering application of the steel slag powder are seriously restricted.
On the other hand, in recent years, the annual emission of sulfur dioxide in China is about 2000 million tons. The loss of nitrogen oxides and sulfur oxides to China is over billions of yuan each year, and the pollutants are mainly from smoke discharged by coal-fired boilers, smelting, sintering and other industries. In order to reduce environmental pollution, pollutants such as sulfur dioxide in the flue gas are generally removed and then the flue gas can be discharged into the atmosphere. At present, large-scale electric power and metallurgyThe desulphurization facilities built and put into operation by enterprises basically adopt wet, dry and semi-dry desulphurization technologies of Ca systems, and the main chemical component of the generated desulphurization by-product is CaSO 4 、CaSO 3 、CaCO 3 And CaO. For the byproducts, a good disposal mode is not provided at present, stacking and landfill are mainly used, industrial land is occupied, and secondary pollution to water sources, soil and atmosphere is caused due to improper disposal.
How to realize more efficient utilization of the waste steel slag and effective treatment of the flue gas desulfurization by-products becomes a difficult problem to be solved urgently in the industry.
Disclosure of Invention
The main purpose of the application is to provide a desulfurization method for mixing steel slag, clay and limestone for pulping and a mixed desulfurizer, so as to overcome the defects in the prior art.
In order to achieve the above purpose, the present application adopts a technical solution comprising:
one aspect of the present application provides a mixed desulfurization agent, which includes 45wt% to 55wt% of waste steel slag, 25wt% to 35wt% of clay, and 15wt% to 25wt% of limestone.
In one embodiment, the waste steel slag, the clay and the limestone are all granular and have a particle size of less than 100 meshes, such as 100-200 meshes.
In one embodiment, the clay comprises attapulgite clay.
Another aspect of the present application provides a desulfurization slurry, which comprises the mixed desulfurization agent and water, wherein the desulfurization slurry has a solid content of 10wt% to 15wt% and a pH value of 8.5 or more.
In the application, the waste steel slag is waste slag discharged in a steel making process, the chemical components of the waste steel slag mainly comprise oxides of silicon, calcium, magnesium, iron and the like, and the main phase components of the waste steel slag comprise tricalcium silicate, dicalcium silicate, calcium ferrite, iron oxide and the like.
In this application, the clay is typically formed from aluminosilicate minerals after weathering on the earth's surface, but some diagenesis also produces clay. Preferably, the clay is attapulgite clay, which is called attapulgite clay for short, and has a soil block structure and is grey white, grey green, light yellow and light green in color. The grease has the advantages of luster, light specific gravity, 2-3 grades of Mohs hardness, viscosity and plasticity when being wet, small drying shrinkage, no cracking, strong water absorption, over 150 percent and pH value of about 8.5.
In this application, limestone is a natural material with a main component of CaCO 3 Can react with sulfur dioxide gas under certain conditions, thereby achieving the aim of desulfurization.
In the mixed desulfurizer of the application, the equal reserves of main components such as steel slag, clay, limestone are huge, and the homoenergetic takes place to react with sulfur dioxide in the flue gas to realize the desulfurization. In particular, the desulfurization slurry is prepared by mixing steel slag, clay and limestone according to a certain proportion, wherein a large amount of alkaline substances are contained, and the alkaline substances can be mixed with SO 2 The reaction takes place. The uniform mixture of the steel slag, the clay and the limestone is used as a desulfurizer, so that the desulfurization cost can be reduced, the steel slag can be comprehensively utilized, and the purpose of treating wastes with processes of wastes against one another is achieved.
Another aspect of the application provides a method for desulfurization of mixed slurrying of steel slag, clay and limestone, which comprises the following steps:
(1) After impurity removal and crushing treatment are carried out on the waste steel slag, the clay and the limestone, and then the waste steel slag, the clay and the limestone are uniformly mixed to prepare the mixed desulfurizer;
(2) Uniformly mixing the mixed desulfurizer prepared in the step (1) with water to prepare the desulfurization slurry;
(3) And (3) enabling the sulfur-containing flue gas to be fully contacted with the desulfurization slurry prepared in the step (2), and realizing desulfurization treatment on the sulfur-containing flue gas.
In one embodiment, the desulfurization method specifically includes:
(1) Removing impurities from the waste steel slag, clay and limestone, drying and crushing the waste steel slag, the clay and the limestone in sequence, and uniformly mixing the obtained waste steel slag particles, clay particles and limestone particles to prepare a mixed desulfurizer;
(2) Uniformly mixing the mixed desulfurizer with water in a reaction tower to prepare the desulfurization slurry;
(3) Inputting sulfur-containing flue gas into the reaction tower from the lower part of the reaction tower, and enabling the sulfur-containing flue gas to be in full contact with the desulfurization slurry in the reaction tower and react with the desulfurization slurry, so that at least part of sulfur-containing components in the sulfur-containing flue gas are removed, and then discharging the flue gas subjected to desulfurization treatment from a flue gas discharge port of the reaction tower;
wherein the sulfur-containing component comprises sulfur dioxide.
In one embodiment, the reaction tower is plural, and the step (3) further comprises: enabling the sulfur-containing flue gas to sequentially pass through a plurality of reaction towers, fully contacting and reacting with the desulfurization slurry in each reaction tower until the composition of the flue gas reaches the emission standard, and then discharging the flue gas into the atmosphere from a flue gas discharge port of the last reaction tower.
In one embodiment, step (3) further comprises: and when the pH value of the desulfurization slurry in the reaction tower is reduced to 4-5, discharging the desulfurization slurry serving as waste liquid to a waste liquid pool, and putting the desulfurization slurry with the pH value of more than 8.5 into the reaction tower again.
In one embodiment, step (3) further comprises: and a stirrer is arranged in the reaction tower to fully stir the desulfurization slurry in the reaction tower.
In one embodiment, the desulfurization method further comprises: and separating solid phase substances from the waste liquid, drying, and then applying to the preparation of building materials.
Another aspect of the present application provides a desulfurization system, comprising:
a mixed desulfurization agent production unit comprising:
a first dryer for drying the waste steel slag, clay and limestone,
a particle crusher for crushing the dried waste steel slag, clay and limestone,
the feeding machine is used for inputting a mixed desulfurizer into the reaction tower, and the mixed desulfurizer is mainly formed by uniformly mixing crushed waste steel slag, clay and limestone;
the reaction tower comprises at least one reaction tower, wherein a feed port and a water inlet are arranged at the upper part of the reaction tower, a flue gas discharge port is arranged at the upper part or the middle part of the reaction tower, a flue gas inlet and a liquid discharge port are arranged at the lower part of the reaction tower, the feed port, the water inlet and the flue gas inlet are respectively connected with a feed machine, a water conveying pipeline and a sulfur-containing flue gas generating source and are respectively used for inputting a mixed desulfurizer, water and sulfur-containing flue gas into an inner cavity of the reaction tower, the flue gas discharge port is used for discharging the flue gas subjected to desulfurization treatment out of the reaction tower, the liquid discharge port is used for discharging waste liquid out of the reaction tower, the waste liquid is generated after desulfurization slurry and the sulfur-containing flue gas are fully contacted and reacted, the pH value of the waste liquid is 4-5, and the desulfurization slurry is mainly formed by mixing the mixed desulfurizer and the water.
In one embodiment, the feeder may be a crawler feeder or other feeding device, and is not limited thereto.
In one embodiment, the sulfur-containing flue gas generating source includes, but is not limited to, a sintering furnace, a thermal power plant, an industrial boiler, a coal chemical plant, a steel plant, and the like.
In one embodiment, the desulfurization system includes a plurality of reaction towers arranged in series. Particularly, the smoke discharge port of the upper-stage reaction tower is connected with the smoke inlet of the lower-stage reaction tower. In this case, the upper reaction column corresponds to the sulfur-containing flue gas generating source of the lower reaction column.
In one embodiment, the reaction tower is also provided with a stirrer, and the stirrer is used for fully stirring the desulfurization slurry in the reaction tower.
In one embodiment, the desulfurization system may further include a waste liquid tank for containing the waste liquid discharged from the reaction tower.
In one embodiment, the desulfurization system may also include other ancillary equipment, such as devices for separating solids from the spent solution in the lagoon, devices for drying and subsequent processing of the solids, and the like.
In addition, the desulfurization system may further include various temperature detection devices, humidity detection devices, pressure detection devices, pH detection devices, flue gas component analysis devices, and the like, which are configured with the reaction tower, and various valves, flow meters, and the like, which are configured with the water delivery pipeline and the flue gas delivery pipeline, and these devices may all adopt devices known in the art and are set in the desulfurization system according to a manner known in the art, and thus, the description thereof is omitted.
Compared with the prior art, the technical scheme of the application has the advantages that:
(1) The mixed desulfurizer is prepared from the waste steel slag mixed clay, the limestone and the like, so that the raw material source is wide, the cost is low, the waste steel slag can be effectively utilized, sulfur-containing components such as sulfur dioxide in sulfur-containing flue gas can be removed by the mixed desulfurizer at high efficiency and low cost, and the purpose of treating waste with waste is achieved.
(2) The mixed desulfurizer has the advantages of small particles, convenience in processing and the like for byproducts generated after sulfur-containing flue gas desulfurization, can be used as raw materials in cement plants and building industries, can be used for producing products such as cement, bricks and tiles, does not generate secondary pollution, and realizes comprehensive utilization of resources.
Drawings
FIG. 1 is a schematic diagram of a desulfurization system in one embodiment of the present application;
description of reference numerals: 1-sulfur-containing flue gas generating source; 2-a control valve; 3-a reaction tower; 4-a waste liquid pool; 5-a flow pump; 6-a stirrer; 7-a flue gas analyzer; 8-crawler feeding machine; 9-a particle grinder; 10-clean flue gas discharge port; 11-a first dryer; 12-a second dryer; 13-cement plant; 14-brickyard.
Detailed Description
The technical solutions of the present application will be explained in more detail below with reference to several embodiments, but these detailed descriptions are only used to teach those skilled in the art how to implement the present application, and are not intended to exhaust all feasible ways of the present application and are not intended to limit the scope of the present application.
Example 1
The embodiment provides a method for desulfurization by mixing steel slag, clay and limestone for pulping, which mainly comprises the following steps: firstly, removing impurities from waste converter steel slag, attapulgite clay and limestone, crushing, uniformly mixing according to a proportion to prepare a mixed desulfurizer, and uniformly mixing the mixed desulfurizer with water to prepare a desulfurization slurry; then the sulfur-containing flue gas is fully contacted with the desulfurization slurry, thereby realizing the desulfurization treatment of the sulfur-containing flue gas.
In the present embodiment, the desulfurization method is mainly implemented based on the desulfurization system shown in fig. 1, and the desulfurization system mainly includes a reaction tower 3, a waste liquid pool 4, a stirrer 6, a crawler feeder 8, a particle crusher 9, a first dryer 11, and the like. The reaction towers 3 may be two or more and arranged in series in multiple stages.
Further, the desulfurization method specifically comprises the following steps:
s1, carry out edulcoration processing respectively to abandonment steel slag, clay, lime stone according to conventional mode, later carry out drying process to abandonment steel slag, attapulgite clay, lime stone respectively with first drying-machine 11 to get rid of the moisture in steel slag and clay, the lime stone, prevent to become the mud form when it gets into rubbing crusher, guarantee to realize better shredding.
S2, respectively crushing the waste steel slag, the clay and the limestone processed in the step S1 into particles with the diameter smaller than 100 meshes by using a particle crusher 9, so that the specific surface area of the components of the mixed desulfurizer can be remarkably improved, the components are more easily and fully mixed, and the desulfurization efficiency can be improved in a desulfurization process. Then evenly mixing the granular waste steel slag, clay and limestone according to the mass ratio of about 5: 3: 2 to prepare the mixed desulfurizer.
And S3, inputting the mixed desulfurizer prepared in the step S2 into the reaction towers 3 from the feeding ports at the tops of the reaction towers 3 through crawler feeding machines 8, and simultaneously inputting water into the reaction towers 3 from the water inlets at the tops of the reaction towers 3 through water pipelines. The water pipeline is provided with a flow pump 5 which is used for proportioning according to the amount of the mixed desulfurizer entering the reaction tower so as to supply water with proper volume, so that the mixed desulfurizer entering the reaction tower is mixed with the water to prepare the desulfurization slurry with solid content of about 10wt% and pH value of more than 8.5. In order to prevent the waste steel slag, the clay and the limestone from precipitating in the desulfurization slurry and ensure the full reaction and uniform mixing of the three, the stirrer 6 is preferably arranged in the reaction tower for full stirring.
And S4, providing sulfur-containing flue gas by using the sulfur-containing flue gas generating source 1, enabling the sulfur-containing flue gas to enter the reaction tower from a flue gas inlet arranged at the lower part of the side surface of the reaction tower 3 after passing through a flue gas conveying pipeline with a control valve 2, contacting and fully reacting with desulfurization slurry in the reaction tower, at least partially removing components such as sulfur dioxide in the sulfur-containing flue gas, enabling the desulfurized flue gas to flow upwards in the reaction tower, and discharging the desulfurized flue gas from a flue gas discharge port positioned at the middle upper part of the reaction tower. In order to prevent the required desulfurization effect from being achieved in one desulfurization process, a second reaction tower or more reaction towers are preferably arranged for desulfurization again, as shown in fig. 1, namely, the desulfurized flue gas discharged from the first reaction tower enters the flue gas inlet of the second reaction tower and is fully contacted with the desulfurization slurry again, and the like until the flue gas is discharged from the flue gas discharge port of the last reaction tower. The flue gas discharge port of this last reaction tower can be defined as net flue gas discharge port 10, and this net flue gas discharge port 10 department can set up smoke analyzer 7 for detect the chemical composition of flue gas after last reaction tower desulfurization treatment, in order to confirm whether it reaches the emission requirement, the flue gas after the desulfurization that reaches emission standard discharges into the atmosphere through net flue gas discharge port 10.
In this step, when the desulfurization slurry in any one of the reaction towers sufficiently absorbs sulfur dioxide and other components in the flue gas and has a pH of 4 to 5, the desulfurization effect is lowered, and the slurry cannot be continuously absorbed and used, and becomes a waste liquid. The waste liquid can be discharged into the waste liquid tank 4 through a liquid outlet provided at the lower part of the reaction tower 3 and a control valve fitted thereto.
Further, the desulfurization system may further include a second dryer 12, a cement plant 13, a brick plant 14, and the like. And the desulfurization method may further include:
carry out abundant sedimentation treatment to the waste liquid that gets into waste liquid pond 4, make solid matter (mainly be waste steel slag, the reaction product of sulfur dioxide etc. in clay and lime and the flue gas, desulfurization product promptly) deposit waste liquid bottom of the pool, discharge clear water in upper strata, send the precipitate of lower floor into second drying-machine 12 and handle, the product after the processing is the raw and other materials of a fine building trade, it is little to have the granule, advantages such as the processing of being convenient for, can send to cement plant 13, department such as brick and tile factory 14 utilizes as raw materials for production, and can further process into cement product, brick and tile etc..
By measuring the sulfur content in the desulfurization product by a barium sulfate gravimetric method (GB/T176-1996), it can be found that the sulfur-fixing efficiency eta of the mixed desulfurizer of the embodiment can reach about 81%. Eta = S 1 ×M 1 /(S 0 ×M 0 )×100％。M 0 、M 1 The mass of the sample before and after calcination, respectively, is given in g. S 0 、S 1 The sulfur content (converted to sulfur trioxide mass percent) of the sample before and after calcination is shown.
Comparative example 1
The structure of the desulfurization system provided in this comparative example is substantially the same as that of example 1, and the desulfurization method used is similar to that of example except that: only the crushed waste steel slag particles are used as a desulfurizer. The sulfur-fixing efficiency of the desulfurizing agent of the comparative example is about 10%.
Comparative example 2
The structure of the desulfurization system provided in this comparative example is substantially the same as that of example 1, and the desulfurization method used is also similar to that of example, except that: only the crushed limestone and attapulgite clay are mixed to be used as a desulfurizer. The sulfur-fixing efficiency of the desulfurizing agent of the comparative example is about 53%.
Comparative example 3
The structure of the desulfurization system provided in this comparative example is substantially the same as that of example 1, and the desulfurization method used is similar to that of example except that: only the crushed waste steel slag and limestone are mixed to be used as a desulfurizer. The sulfur fixation efficiency of the desulfurizing agent of the comparative example is about 42%.
Comparative example 4
The structure of the desulfurization system provided in this comparative example is substantially the same as that of example 1, and the desulfurization method used is also similar to that of example, except that: only the crushed waste steel slag particles are mixed with attapulgite clay to be used as a desulfurizer. The sulfur-fixing efficiency of the desulfurizing agent of the comparative example is about 25%.
Example 2 the desulfurization process of this example is substantially the same as that of example 1, except that: the mass ratio of the waste steel slag, the clay and the limestone in the mixed desulfurizer is 11: 5: 4. The sulfur-fixing efficiency of the mixed desulfurizing agent of the embodiment is about 78%.
Example 3 the desulfurization process of this example is essentially the same as that of example 1, except that: the mass ratio of the waste steel slag, the clay and the limestone in the mixed desulfurizer is 9: 6: 5. The sulfur-fixing efficiency of the mixed desulfurizing agent of the embodiment is about 80%.
In addition, the hardness, compressive strength, etc. of the cement products and tiles produced using the desulfurization products of examples 1 to 3 were higher than those of ordinary cement products and tiles by 20% or more.
This application is through using slag, clay and lime stone as raw and other materials, with it dry, smash back proportional mixing, mix with water again and make the desulfurization thick liquid, later utilize the desulfurization thick liquid as the absorbent, realized wet flue gas desulfurization, it can be applied to the sulfur dioxide absorption of thermal power plant, industry coal fired boiler and other sulfur dioxide containing flue gas and handles. The desulfurization slurry can achieve the purpose of completely absorbing components such as sulfur dioxide in flue gas, avoids environmental pollution caused by stacking of a large amount of steel slag, improves the environmental protection effect, and effectively saves resources. The desulfurization slurry after absorbing the sulfur-containing components in the flue gas can be separated into desulfurization products after being treated by precipitation and the like, and the desulfurization products can be used as building raw materials and have the advantages of low price, high strength and the like.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present application, and are intended to enable those skilled in the art to understand the contents of the present application and implement the present application, and not to limit the scope of the present application. All equivalent changes and modifications made according to the spirit of the present application should be covered in the protection scope of the present application.
Claims (10)
1. A mixed desulfurizer is characterized by comprising 45wt% -55wt% of waste steel slag, 25wt% -35wt% of clay and 15wt% -25wt% of limestone.
2. The mixed desulfurization agent according to claim 1, characterized in that: the waste steel slag, the clay and the limestone are all granular, and the particle size is less than 100 meshes.
3. The mixed desulfurization agent according to claim 1 or 2, characterized in that: the clay comprises attapulgite clay.
4. A desulfurization slurry characterized by comprising the mixed desulfurization agent according to any one of claims 1 to 3 and water, and having a solid content of 10 to 15wt% and a pH value of 8.5 or more.
5. The method for mixing, pulping and desulfurizing steel slag, clay and limestone is characterized by comprising the following steps of:
(1) The waste steel slag, clay and limestone are subjected to impurity removal and crushing treatment and then are uniformly mixed to prepare the mixed desulfurizer as claimed in any one of claims 1 to 3;
(2) Uniformly mixing the mixed desulfurizer prepared in the step (1) with water to prepare the desulfurization slurry of claim 4;
(3) And (3) enabling the sulfur-containing flue gas to be fully contacted with the desulfurization slurry prepared in the step (2), and realizing desulfurization treatment on the sulfur-containing flue gas.
6. The method for pulping and desulfurizing the steel slag, the clay and the limestone by mixing according to claim 5, which is characterized by comprising the following steps of:
(1) Removing impurities from the waste steel slag, clay and limestone, drying and crushing the waste steel slag, the clay and the limestone in sequence, and uniformly mixing the obtained waste steel slag particles, the clay particles and the limestone particles to prepare a mixed desulfurizer;
(2) Uniformly mixing the mixed desulfurizer with water in a reaction tower to prepare the desulfurization slurry;
(3) Inputting sulfur-containing flue gas into the reaction tower from the lower part of the reaction tower, and enabling the sulfur-containing flue gas to be in full contact with the desulfurization slurry in the reaction tower and react with the desulfurization slurry, so that at least part of sulfur-containing components in the sulfur-containing flue gas are removed, and then discharging the flue gas subjected to desulfurization treatment from a flue gas discharge port of the reaction tower;
wherein the sulfur-containing component comprises sulfur dioxide.
7. The method for pulping and desulfurizing steel slag, clay and limestone as claimed in claim 6, wherein the reaction tower is provided in plurality, and the step (3) further comprises: enabling the sulfur-containing flue gas to sequentially pass through a plurality of reaction towers, fully contacting and reacting with the desulfurization slurry in each reaction tower until the composition of the flue gas reaches the emission standard, and then discharging the flue gas into the atmosphere from a flue gas discharge port of the last reaction tower.
8. The method for pulping and desulfurizing steel slag, clay and limestone mixed according to claim 6, wherein the step (3) further comprises: and when the pH value of the desulfurization slurry in the reaction tower is reduced to 4-5, discharging the desulfurization slurry serving as waste liquid to a waste liquid pool, and putting the desulfurization slurry with the pH value of more than 8.5 into the reaction tower again.
9. The method for pulping and desulfurizing steel slag, clay and limestone as claimed in any one of claims 6 to 8, wherein the step (3) further comprises: and a stirrer is arranged in the reaction tower to fully stir the desulfurization slurry in the reaction tower.
10. The method for pulping and desulfurizing steel slag, clay and limestone in a mixing manner according to claim 8, further comprising the following steps: and separating solid phase substances from the waste liquid, drying, and then applying to the preparation of building materials.
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