CN115400577B - Method for pulping and desulfurizing steel slag, clay and limestone by mixing and mixed desulfurizing agent - Google Patents
Method for pulping and desulfurizing steel slag, clay and limestone by mixing and mixed desulfurizing agent Download PDFInfo
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- CN115400577B CN115400577B CN202211069360.8A CN202211069360A CN115400577B CN 115400577 B CN115400577 B CN 115400577B CN 202211069360 A CN202211069360 A CN 202211069360A CN 115400577 B CN115400577 B CN 115400577B
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 66
- 239000002893 slag Substances 0.000 title claims abstract description 66
- 239000010959 steel Substances 0.000 title claims abstract description 66
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 61
- 239000004927 clay Substances 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 235000019738 Limestone Nutrition 0.000 title claims abstract description 46
- 239000006028 limestone Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002156 mixing Methods 0.000 title claims abstract description 21
- 238000004537 pulping Methods 0.000 title claims abstract description 11
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 87
- 230000023556 desulfurization Effects 0.000 claims abstract description 86
- 239000003546 flue gas Substances 0.000 claims abstract description 71
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002699 waste material Substances 0.000 claims abstract description 59
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011593 sulfur Substances 0.000 claims abstract description 42
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 42
- 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 68
- 239000002002 slurry Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 238000011282 treatment Methods 0.000 claims description 17
- 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
- 239000012535 impurity Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000011449 brick Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000010808 liquid waste Substances 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
- 239000000779 smoke Substances 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
- 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
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000010298 pulverizing process Methods 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
- -1 buildings Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 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
- 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
- 238000004140 cleaning Methods 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
- 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
- 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 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
- 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
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
Landscapes
- 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 method for pulping and desulfurizing steel slag, clay and limestone by mixing and a mixed desulfurizing agent. The mixed desulfurizing agent comprises waste steel slag particles, clay particles and limestone particles which are uniformly mixed. The mixed desulfurizing agent is prepared from the waste steel slag mixed clay, limestone and the like, so that the raw material sources are wide, the cost is low, the waste steel slag can be effectively utilized, and the components such as sulfur dioxide in sulfur-containing flue gas can be efficiently removed by the mixed desulfurizing agent at low cost, so that the purpose of treating waste by waste is achieved; meanwhile, the mixed desulfurizing agent has the advantages of small particles, convenient processing and the like on byproducts after sulfur-containing flue gas desulfurization, can be used as raw materials in cement factories and construction industries, does not produce secondary pollution, and the prepared building material also has the advantages of high strength, low cost and the like, and realizes comprehensive utilization of resources.
Description
Technical Field
The application relates to a flue gas desulfurization method, in particular to a steel slag, clay and limestone mixed pulping desulfurization method and a mixed desulfurizing agent, and belongs to the technical field of environmental protection.
Background
In 2020, the crude steel yield in China exceeds 10 hundred million tons, and the correspondingly produced steel slag accounts for 10% -15% of the crude steel yield, namely, the steel slag yield exceeds 1 hundred million tons. However, the comprehensive utilization rate of the steel slag is not high at present, and only about 30 percent, so that a large amount of steel slag is produced and cannot be utilized each year, and the steel slag occupies a large land area, and more serious, causes environmental pollution. The existing effective way for utilizing the steel slag with large total amount and high added value is to produce steel slag powder, and the steel slag powder is applied to building materials, buildings, concrete, roads and the like, but the existing technology for producing the steel slag powder by utilizing 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 severely restricts the large-scale production and engineering application of the steel slag powder.
On the other hand, the annual emission of sulfur dioxide in China in recent years is about 2000 ten thousand tons. The loss of nitrogen oxides and sulfur oxides to China is more than one hundred billion yuan each year, and the pollutants are mainly from flue gas discharged by industries such as coal-fired boilers, smelting, sintering and the like. In order to reduce environmental pollution, pollutants such as sulfur dioxide in the flue gas are generally removed and then discharged into the atmosphere. At present, a wet, dry and semi-dry desulfurization technology of Ca is basically adopted for the desulfurization facilities built into operation of large-scale electric power and metallurgical enterprises, and the main chemical components of the desulfurization byproducts are CaSO 4 、CaSO 3 、CaCO 3 CaO. For the byproducts, no good disposal mode exists at present, but stacking and landfill are mainly adopted, so that the industrial land is occupied, and secondary pollution is caused to water sources, soil and atmosphere due to inadequate treatment.
How to realize more efficient utilization of waste steel slag and effective disposal of flue gas desulfurization byproducts has become a difficult problem to be solved in the industry.
Disclosure of Invention
The main purpose of the application is to provide a steel slag, clay and limestone mixed pulping desulfurization method and a mixed desulfurizing agent, so as to overcome the defects in the prior art.
In order to achieve the above object, the present application adopts the technical scheme that:
one aspect of the present application provides a mixed desulfurizing agent comprising 45wt% to 55wt% waste steel slag, 25wt% to 35wt% clay, and 15wt% to 25wt% limestone.
In one embodiment, the waste steel slag, clay, and limestone are all granular and have a particle size of 100 mesh or less, for example 100 mesh to 200 mesh.
In one embodiment, the clay comprises attapulgite clay.
In another aspect, the present application provides a desulfurization slurry, which includes the mixed desulfurization agent and water, wherein the solid content of the desulfurization slurry is 10wt% to 15wt% and the pH value is above 8.5.
In the application, the waste steel slag is waste slag discharged in the steelmaking process, the chemical components are mainly oxides of silicon, calcium, magnesium, iron and the like, and the main phase composition is tricalcium silicate, dicalcium silicate, calcium ferrite, ferric oxide and the like.
In this application, the clay is typically formed from aluminosilicate minerals after weathering at the earth's surface, but some diagenetic effects may also produce clay. Preferably, the clay is attapulgite clay, which is simply called attapulgite, has a soil block structure and is gray, grey, light yellow and light green. The grease has the advantages of luster, light specific gravity, 2-3 levels of Mohs hardness, adhesiveness and plasticity when wet, small drying shrinkage, no cracking, strong water absorption, more than 150 percent and pH value of about 8.5.
In the present application, the limestone is a natural material whose main component is CaCO 3 Can react with sulfur dioxide gas under certain conditions, thereby achieving the purpose of desulfurization.
In the mixed desulfurizing agent, main components such as steel slag, clay, limestone and the like have huge reserves and can react with sulfur dioxide in flue gasThereby realizing desulfurization. In particular, the desulfurization slurry is prepared by mixing steel slag, clay and limestone according to a certain proportion, and contains a large amount of alkaline substances which 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 the desulfurizing agent, so that the desulfurizing cost can be reduced, the steel slag can be comprehensively utilized, and the purpose of treating waste by waste is achieved.
Another aspect of the present application provides a method for pulping and desulfurizing steel slag, clay and limestone by mixing, comprising:
(1) Removing impurities from the waste steel slag, clay and limestone, crushing, and uniformly mixing to obtain the mixed desulfurizing agent;
(2) Uniformly mixing the mixed desulfurizing agent prepared in the step (1) with water to prepare the desulfurizing slurry;
(3) And (3) fully contacting the sulfur-containing flue gas with the desulfurization slurry prepared in the step (2) to realize desulfurization treatment of the sulfur-containing flue gas.
In one embodiment, the desulfurization method specifically includes:
(1) The waste steel slag, clay and limestone are subjected to impurity removal treatment, then are sequentially subjected to drying and crushing treatment, and the obtained waste steel slag particles, clay particles and limestone particles are uniformly mixed to prepare a mixed desulfurizing agent;
(2) Uniformly mixing the mixed desulfurizing agent and water in a reaction tower to prepare the desulfurizing slurry;
(3) Inputting sulfur-containing flue gas into the reaction tower from the lower part of the reaction tower, enabling the sulfur-containing flue gas to fully contact and react with desulfurization slurry in the reaction tower, thereby removing at least part of sulfur-containing components in the sulfur-containing flue gas, 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 a plurality of, and the step (3) further comprises: the sulfur-containing flue gas sequentially passes through the reaction towers, and fully contacts and reacts with the desulfurization slurry in each reaction tower until the composition of the flue gas reaches the emission standard, and the flue gas is discharged into the atmosphere from a flue gas discharge port of the last reaction tower.
In one embodiment, step (3) further comprises: when the pH value of the desulfurization slurry in the reaction tower is reduced to 4-5, the desulfurization slurry is discharged to a waste liquid pool as waste liquid, and the desulfurization slurry with the pH value of more than 8.5 is placed in the reaction tower again.
In one embodiment, step (3) further comprises: a stirrer is provided in the reaction tower to sufficiently stir the desulfurization slurry in the reaction tower.
In one embodiment, the desulfurization method further comprises: separating out solid phase matters in the waste liquid, drying, and then applying to preparing building materials.
Another aspect of the present application provides a desulfurization system comprising:
a mixed desulfurizing agent production unit comprising:
the first dryer is used for drying the waste steel slag, clay and limestone,
a particle pulverizer for pulverizing the dried waste steel slag, clay and limestone,
the batch feeder is used for inputting a mixed desulfurizing agent into the reaction tower, and the mixed desulfurizing agent is mainly formed by uniformly mixing crushed waste steel slag, clay and limestone;
the device comprises at least one reaction tower, wherein a feed inlet and a water inlet are arranged on the upper part of the reaction tower, a flue gas discharge outlet is arranged on the upper part or the middle part of the reaction tower, a flue gas inlet and a liquid discharge outlet are arranged on the lower part of the reaction tower, the feed inlet, 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 mixed desulfurizing agent, water and sulfur-containing flue gas into the inner cavity of the reaction tower, the flue gas discharge outlet is used for discharging flue gas after desulfurization treatment out of the reaction tower, the liquid discharge outlet is used for discharging liquid waste out of the reaction tower, the liquid waste is generated after desulfurization slurry fully contacts and reacts with sulfur-containing flue gas, the pH value of the liquid waste is 4-5, and the desulfurization slurry is mainly formed by mixing the mixed desulfurizing agent and the water.
In one embodiment, the feeder may employ a crawler feeder or other feeder 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 coalification plant, a steel mill, and the like.
In one embodiment, the desulfurization system includes a plurality of reaction towers arranged in series. Specifically, the flue gas discharge port of the upper-stage reaction tower is connected with the flue gas inlet of the lower-stage reaction tower. In this case, the upper-stage reaction tower corresponds to a sulfur-containing flue gas generating source of the lower-stage reaction tower.
In one embodiment, a stirrer is further arranged in the reaction tower, 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 waste liquid discharged from the reaction tower.
In one embodiment, the desulfurization system can also include other associated equipment, such as devices for separating solids from the waste stream in the waste stream tank, devices for drying and subsequent processing of the solids, and the like.
In addition, the desulfurization system may further include various temperature detecting devices, humidity detecting devices, pressure detecting devices, pH detecting devices, smoke component analyzing devices, etc. which are configured to be matched with the reaction tower, and various valves, flow meters, etc. which are configured to be matched with the water conveying pipeline and the smoke conveying pipeline, all of which may be devices known in the art and are configured in the desulfurization system according to the manner known in the art, so that the description thereof will not be repeated here.
Compared with the prior art, the technical scheme has the advantages that:
(1) The mixed desulfurizing agent is prepared from the waste steel slag mixed clay, limestone and the like, so that the raw material sources are 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 efficiently removed by the mixed desulfurizing agent at low cost, and the purpose of treating waste by waste is achieved.
(2) The mixed desulfurizing agent has the advantages of small particles, convenient processing and the like on byproducts after sulfur-containing flue gas desulfurization, can be used as raw materials in cement factories and construction industries, can be used for producing products such as cement, bricks and tiles, does not produce secondary pollution, and realizes comprehensive utilization of resources.
Drawings
FIG. 1 is a schematic view of a desulfurization system according to an embodiment of the present application;
reference numerals illustrate: 1-a 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-a crawler batch feeder; 9-a particle mill; 10-cleaning a smoke discharge port; 11-a first dryer; 12-a second dryer; 13-cement plant; 14-brickwork.
Detailed Description
The technical solutions of the present application will be explained in more detail below with reference to several embodiments, but these specific descriptions are only for illustrating how those skilled in the art can practice the present application, and are not intended to be exhaustive of all possible ways of the present application nor to limit the scope of the present application.
Example 1
The embodiment provides a steel slag, clay and limestone mixed pulping desulfurization method, which mainly comprises the following technical processes: firstly, removing impurities from waste converter steel slag, attapulgite clay and limestone, crushing, uniformly mixing according to a proportion to obtain a mixed desulfurizing agent, and uniformly mixing the mixed desulfurizing agent with water to obtain desulfurization slurry; and then the sulfur-containing flue gas is fully contacted with the desulfurization slurry, so that the desulfurization treatment of the sulfur-containing flue gas is realized.
In the present embodiment, the desulfurization method is mainly carried out based on the desulfurization system shown in fig. 1, which mainly includes a reaction tower 3, a waste liquid tank 4, a stirrer 6, a crawler feeder 8, a particle pulverizer 9, a first dryer 11, and the like. The reaction tower 3 may be two or more and may be arranged in series in multiple stages.
Further, the desulfurization method specifically comprises the following steps:
s1, carrying out impurity removal treatment on waste steel slag, clay and limestone respectively in a conventional manner, and then carrying out drying treatment on the waste steel slag, attapulgite clay and limestone respectively by using a first dryer 11 so as to remove water in the steel slag, the clay and the limestone, prevent the water from becoming slurry when entering a pulverizer, and ensure that better pulverizing treatment can be realized.
S2, the waste steel slag, clay and limestone processed in the step S1 are respectively crushed by a particle crusher 9 until the particle diameter is smaller than 100 meshes, so that the specific surface area of the mixed desulfurizer components can be remarkably improved, the mixed desulfurizer components are easier to fully mix, and the desulfurization efficiency can be improved in a desulfurization process. And uniformly mixing the granular waste steel slag, clay and limestone according to the mass ratio of about 5:3:2 to prepare the mixed desulfurizing agent.
S3, the mixed desulfurizing agent prepared in the step S2 is input into the reaction towers 3 through a crawler feeder 8 from a feed inlet at the top of each reaction tower 3, and meanwhile, water is input into the reaction towers 3 through a water conveying pipeline from a water inlet at the top of each reaction tower 3. The water pipe is provided with a flow pump 5 for proportioning according to the amount of the mixed desulfurizing agent entering the reaction tower so as to supply water with proper volume, so that the mixed desulfurizing agent entering the reaction tower is mixed with the water to prepare desulfurizing slurry with solid content of about 10wt% and pH value of above 8.5. In order to prevent the waste steel slag, clay and limestone from precipitating in the desulfurization slurry and ensure the full reaction and uniform mixing of the waste steel slag, clay and limestone, a stirrer 6 is preferably arranged in the reaction tower for full stirring.
S4, providing sulfur-containing flue gas by using a 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, enabling the sulfur-containing flue gas to fully react with desulfurization slurry in the flue gas, so that sulfur dioxide and other components in the sulfur-containing flue gas are at least partially removed, and enabling the desulfurized flue gas to flow upwards in the reaction tower and be discharged from a flue gas discharge port positioned at the upper middle part of the reaction tower. In order to prevent the desulfurization process from failing to achieve the desired desulfurization effect, it is preferable to provide a second reaction tower or more reaction towers for re-desulfurization, as shown in fig. 1, i.e., to allow the desulfurized flue gas discharged from the first reaction tower to enter the flue gas inlet of the second reaction tower and to be fully contacted with the desulfurization slurry again, and so on until the flue gas is discharged from the flue gas discharge port of the last reaction tower. The flue gas discharge port of the last reaction tower can be defined as a clean flue gas discharge port 10, and a flue gas analyzer 7 can be arranged at the clean flue gas discharge port 10 and used for detecting chemical components of the flue gas after desulfurization treatment of the last reaction tower so as to determine whether the chemical components reach discharge requirements, and the desulfurized flue gas reaching discharge standards is discharged into the atmosphere through the clean 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 the pH value reaches 4 to 5, the desulfurization effect is reduced, and the desulfurization slurry cannot be absorbed and used continuously, so that the desulfurization slurry becomes waste liquid. The waste liquid can be discharged into a waste liquid pool 4 through a liquid outlet arranged at the lower part of the reaction tower 3 and a control valve matched with the liquid outlet.
Further, the desulfurization system may further include a second dryer 12, a cement plant 13, a brick and tile plant 14, and the like. And the desulfurization method may further include:
the waste liquid entering the waste liquid pond 4 is fully precipitated, so that the solid matters (mainly reaction products of waste steel slag, clay, lime, sulfur dioxide in flue gas and the like, namely desulfurization products) in the waste liquid are precipitated at the bottom of the waste liquid pond, clear water at the upper layer is discharged, the precipitate at the lower layer is sent to the second dryer 12 for treatment, and the treated product is a good raw material in the construction industry, has the advantages of small particles, convenient processing and the like, can be sent to the cement plant 13, the brick and tile plant 14 and the like for utilization as production raw materials, and can be further processed into cement products, bricks and tiles and the like.
The sulfur content in the desulfurization product was measured by the barium sulfate gravimetric method (GB/T176-1996), and it was found that the sulfur fixation efficiency η of the mixed desulfurizing agent of this example could reach about 81%. η=s 1 ×M 1 /(S 0 ×M 0 )×100%。M 0 、M 1 Before and after calcination of the sample, respectivelyThe mass of the product is g. S is S 0 、S 1 The sulfur content (in terms of mass percent of sulfur trioxide) of the sample before and after calcination, respectively.
Comparative example 1
The desulfurization system provided in this comparative example was basically the same in structure as in example 1, and the desulfurization method employed was also similar to that of example, except that: only crushed waste steel slag particles are used as a desulfurizing agent. The sulfur fixation efficiency of the desulfurizing agent of this comparative example was about 10%.
Comparative example 2
The desulfurization system provided in this comparative example was basically the same in structure as in example 1, and the desulfurization method employed was also similar to that of example, except that: only crushed limestone and attapulgite clay are mixed to be used as a desulfurizing agent. The sulfur fixation efficiency of the desulfurizing agent of this comparative example was about 53%.
Comparative example 3
The desulfurization system provided in this comparative example was basically the same in structure as in example 1, and the desulfurization method employed was also similar to that of example, except that: only crushed waste steel slag is mixed with limestone to be used as a desulfurizing agent. The sulfur fixation efficiency of the desulfurizing agent of this comparative example was about 42%.
Comparative example 4
The desulfurization system provided in this comparative example was basically the same in structure as in example 1, and the desulfurization method employed was also similar to that of example, except that: only crushed waste steel slag particles and attapulgite clay are mixed to be used as a desulfurizing agent. The sulfur fixation efficiency of the desulfurizing agent of this comparative example was about 25%.
Example 2 the desulfurization method of this example is substantially the same as that of example 1, except that: the mass ratio of the waste steel slag, clay and limestone in the mixed desulfurizing agent is 11:5:4. The sulfur fixation efficiency of the mixed desulfurizing agent of this example was about 78%.
Example 3 the desulfurization method of this example is substantially the same as that of example 1, except that: the mass ratio of the waste steel slag, clay and limestone in the mixed desulfurizing agent is 9:6:5. The sulfur fixation efficiency of the mixed desulfurizing agent of this example was about 80%.
In addition, the hardness, compressive strength and the like of cement products and bricks prepared by using the desulfurization products of examples 1-3 are higher than those of ordinary cement products and bricks by more than 20%.
According to the method, the steel slag, the clay and the limestone are taken as raw materials, the raw materials are dried and crushed, then mixed in proportion, and mixed with water to prepare the desulfurization slurry, and the desulfurization slurry is taken as an absorbent, so that wet flue gas desulfurization is realized, and the method can be applied to sulfur dioxide absorption treatment of thermal power plants, industrial coal-fired boilers and other sulfur dioxide-containing flue gases. The desulfurization slurry can achieve the purpose of completely absorbing sulfur dioxide and other components in flue gas, avoids environmental pollution caused by piling a large amount of steel slag, improves the environmental protection effect, and simultaneously effectively saves resources. The desulfurization slurry after absorbing the sulfur-containing components in the flue gas can be subjected to precipitation and other treatments to separate desulfurization products, and the 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 embodiments are merely for illustrating the technical concept and features of the present application, and are intended to enable those skilled in the art to understand the content of the present application and implement the same according to the content of the present application, not to limit the protection scope of the present application. All equivalent changes or modifications made in accordance with the spirit of the present application are intended to be included within the scope of the present application.
Claims (6)
1. The method for pulping and desulfurizing the steel slag, clay and limestone by mixing is characterized by comprising the following steps:
(1) Removing impurities from waste steel slag, clay and limestone, crushing, and uniformly mixing to obtain a mixed desulfurizing agent, wherein the mixed desulfurizing agent comprises 45-55wt% of waste steel slag, 25-35wt% of clay and 15-25wt% of limestone, the waste steel slag, clay and limestone are all granular, the grain size is less than 100 meshes, and the clay is attapulgite clay;
(2) Uniformly mixing the mixed desulfurizing agent prepared in the step (1) with water in a reaction tower to prepare desulfurizing slurry, wherein the solid content of the desulfurizing slurry is 10-15 wt% and the pH value is above 8.5;
(3) And inputting sulfur-containing flue gas into a reaction tower from the lower part of the reaction tower, fully contacting and reacting the sulfur-containing flue gas with desulfurization slurry in the reaction tower, thereby removing at least part of sulfur-containing components in the sulfur-containing flue gas, and then discharging the flue gas subjected to desulfurization treatment from a flue gas discharge port of the reaction tower, wherein the sulfur-containing components comprise sulfur dioxide.
2. The method for pulping and desulfurizing the steel slag, the clay and the limestone by mixing according to claim 1 is characterized by comprising the following steps: and (3) carrying out impurity removal treatment on the waste steel slag, clay and limestone, sequentially carrying out drying and crushing treatment, and uniformly mixing the obtained waste steel slag particles, clay particles and limestone particles to obtain the mixed desulfurizing agent.
3. The method for desulfurization of steel slag, clay and limestone mixed slurry according to claim 1, wherein the reaction towers are plural, and the step (3) further comprises: the sulfur-containing flue gas sequentially passes through the reaction towers, and fully contacts and reacts with the desulfurization slurry in each reaction tower until the composition of the flue gas reaches the emission standard, and the flue gas is discharged into the atmosphere from a flue gas discharge port of the last reaction tower.
4. The method for desulfurizing steel slag, clay and limestone by mixing pulping according to claim 1, 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 as waste liquid to a waste liquid tank, and putting the desulfurization slurry with the pH value of more than 8.5 in the reaction tower again.
5. The method for desulfurization of steel slag, clay and limestone slurry according to any one of claims 1-4, wherein step (3) further comprises: a stirrer is provided in the reaction tower to sufficiently stir the desulfurization slurry in the reaction tower.
6. The method for desulfurizing steel slag, clay and limestone by mixing and pulping according to claim 4, further comprising: separating out solid phase matters in the waste liquid, drying, and then applying to preparing building materials.
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