CN117414697B - Medium-temperature flue gas desulfurizing agent for cement kiln and preparation method thereof - Google Patents
Medium-temperature flue gas desulfurizing agent for cement kiln and preparation method thereof Download PDFInfo
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- CN117414697B CN117414697B CN202311745009.0A CN202311745009A CN117414697B CN 117414697 B CN117414697 B CN 117414697B CN 202311745009 A CN202311745009 A CN 202311745009A CN 117414697 B CN117414697 B CN 117414697B
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- 239000004568 cement Substances 0.000 title claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 31
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 31
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003546 flue gas Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 60
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 44
- 230000023556 desulfurization Effects 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003723 Smelting Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 4
- 239000002699 waste material Substances 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 14
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 11
- 239000000378 calcium silicate Substances 0.000 claims description 10
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000428 dust Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010459 dolomite Substances 0.000 abstract description 3
- 229910000514 dolomite Inorganic materials 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 10
- 235000012241 calcium silicate Nutrition 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 5
- 239000000391 magnesium silicate Substances 0.000 description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 description 5
- 235000019792 magnesium silicate Nutrition 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 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
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0233—Other waste gases from cement factories
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to the technical field of cement raw material additives, in particular to a medium-temperature flue gas desulfurizing agent for cement kiln and a preparation method thereof, which is characterized in that based on calcium silicon slag generated by smelting magnesium by a Pidgeon method, a certain amount of red mud is added for mixing modification, and then part of papermaking white mud is added to prepare high-efficiency CaO-SiO 2 ‑Fe 2 O 3 The MgO-based desulfurizer is directly used for removing sulfur dioxide in the cement production process, and solves the problems that the intermediate temperature desulfurization effect of the desulfurizer prepared by adopting other catalysts such as magnesium smelting dust, dolomite and the like in the prior art is poor, the desulfurizer is easy to crust when used for a cement kiln and the like.
Description
Technical Field
The invention relates to the technical field of cement raw material additives, in particular to a medium-temperature flue gas desulfurizing agent for a cement kiln and a preparation method thereof.
Background
Cement is an important support for foundation construction in China.
The cement industry, however, has contributed to the economic development and also brought about a series of problems.
SO 2 Is a main atmospheric pollutant in the tail gas of the cement industrial kiln, can cause environmental problems such as acid rain and the like, and endangers the health of human beings and the survival of animals and plants.
With the continuous improvement of environmental protection requirements, the existing emission standard of atmospheric pollutants in cement industry (GB 4915-2013) clearly stipulates that new cement enterprises and existing cement enterprises respectively start SO in 3 months and 1 month in 2014 and 7 months and 1 month in 2015 2 The discharge amount of (C) is not higher than 200mg/Nm 3 。
Cement enterprises in important areas perform more stringent standards.
In the face of huge emission reduction pressure, effective SO removal is found 2 The method of (2) is important.
SO produced by cement industry 2 Mainly composed of sulfur in raw materials and fuelIs produced by oxidation reaction.
Due to self-desulfurization capability of cement process, alkaline materials in the preheater and the decomposing furnace are used for SO in a high-temperature area 2 Has high capture rate, and sulfide in the raw material can generate oxidative decomposition when passing through the preheaters C2 and C3 (about 300-600 ℃) to generate a large amount of SO 2 Cannot be removed.
The prior desulfurization method in the cement industry mainly utilizes limestone in raw materials to absorb SO 2 The self-emission reduction technology and the dry, semi-dry and wet desulfurization technologies have the defects of high wet and semi-dry desulfurization efficiency and cement kiln crust blockage, and the wet desulfurization can generate wastewater to be further treated.
Thus, dry desulfurization is more suitable for cement kilns than for example.
The Pidgeon process produces a large amount of calcium silicon waste residues, most of the waste residues are not reasonably utilized, but are stacked, so that pollution to soil and underground water is caused to a great extent, and a large amount of fine particles are exposed to air to cause air pollution.
The chemical composition of the calcium-silicon waste residue mainly comprises CaO and SiO 2 Etc. it is mainly made of Ca 2 SiO 4 The content of the composition can reach about 90 percent.
The waste residue contains rich calcium component, has certain volcanic ash activity and alkalinity, and can be used for desulfurization according to the characteristic.
The name of the method for desulfurizing the flue gas by using the reduced magnesium slag is disclosed in the national intellectual property agency of 2010, 5 and 12, and the name of the method for desulfurizing the flue gas by using the magnesium slag is disclosed in publication numbers CN101703886A and 2021, 2 and 26, and a device thereof, CN112403216A, suggests that the magnesium slag can be used as a calcium-based desulfurizing agent for carrying out dry desulfurization at a temperature of 850-950 ℃; the publication No. CN102068898A and the publication No. CN116726691A, publication No. CN111185075A, publication No. CN102068898A and publication No. 2023 and 7, respectively, disclose that magnesium slag and other calcium-based materials can be combined to prepare slurry for use as a low-temperature wet desulfurizing agent, and secondary utilization of magnesium slag can be realized while treating flue gas, but the applicant adds the slurry to a cement kiln to perform medium-temperature desulfurization to find that the use effect is poor and the skinning of the cement kiln is easy to cause.
It can be seen that the dry desulfurization of the original magnesium slag at a high temperature of 850-950 ℃ and the wet desulfurization at a low temperature are best, SO that SO is generated during the preheating period (about 300-600 ℃) of the raw materials for combining the cement production process 2 Can effectively remove the magnesium slag without blocking the cement kiln crust, so the dry desulfurization of the magnesium slag in the middle temperature section needs to be further explored, and the magnesium slag is suitable for flue gas desulfurization of the cement kiln.
A large amount of calcium-based components in the calcium-silicon slag are the basis of desulfurization reaction, but the surface of the original slag is smoother, active sites are fewer, and gas-solid reaction is difficult to carry out on the surface of the slag, so that the desulfurization effect of the original slag is poor, and the average desulfurization rate of the first 10min is only about 50% at 300-400 ℃.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a medium-temperature flue gas desulfurizer for a cement kiln and a preparation method thereof, and the invention is based on calcium silicon slag generated by smelting magnesium by a Pidgeon method, and is mixed and modified by adding a certain amount of red mud, and then part of papermaking white mud is added to prepare the high-efficiency CaO-SiO 2 -Fe 2 O 3 The MgO-based desulfurizer is directly used for removing sulfur dioxide in the cement production process, and solves the problems that the intermediate temperature desulfurization effect of the desulfurizer prepared by adopting other catalysts such as magnesium smelting dust, dolomite and the like in the prior art is poor, the desulfurizer is easy to crust when used for a cement kiln and the like.
Specifically, the preparation method of the medium-temperature flue gas desulfurizing agent for the cement kiln comprises the following steps:
1) Grinding and drying the silicon-calcium slag and the red mud, uniformly mixing to ensure that the grain size is less than 150 mu m to obtain waste residue powder, wherein the silicon-calcium slag is calcium-silicon slag generated by smelting magnesium by a Pidgeon process,
2) Soaking the waste residue powder in an alkali solution, magnetically stirring, then regulating the solution to be neutral, adding MgO accounting for 5-15% of the mass of the waste residue powder and papermaking white mud accounting for 10-20% of the mass of the waste residue powder, continuously stirring, centrifugally washing, drying and grinding to obtain the finished product.
Preferably, the mass ratio of the calcium silicate slag to the red mud in the step 1) is 1:0.2-0.3.
Preferably, step 1) milling is performed by ball milling.
Preferably, the alkali solution in the step 2) is potassium hydroxide solution or sodium hydroxide solution, and the solid-liquid ratio of the waste residue powder to the alkali solution is 1:10-20.
Preferably, the magnetic stirring rotating speed of the step 2) is 300-500r/min, the magnetic stirring temperature is 70-80 ℃, and the magnetic stirring time is 1.5-2.5h.
Preferably, step 2) is continued for a period of 1-2 hours.
Preferably, the drying temperature in the step 2) is 65-80 ℃ and the drying time is 8-10h.
Preferably, step 2) is milled to a particle size of less than 75 μm.
Preferably, the main chemical composition of the flue gas desulfurizing agent is CaO42-67%, siO 2 19-28%、Fe 2 O 3 3-10%、MgO6-20%。
The desulfurization principle of the invention is as follows: the calcium-based component is used as a main body to perform gas-solid reaction with sulfur dioxide to generate calcium sulfate, so that the main desulfurization effect is achieved; after the silicon-based component is activated by alkali, the polymerization degree of the silicon-oxygen four sides is reduced, SO that SO 2 More is adsorbed; meanwhile, the specific surface area of the absorbent is increased, the gaps are increased, the surface is roughened, and more active sites are exposed; aiming at the problem of poor medium-temperature absorption rate of the silicon-calcium slag, a certain amount of iron-based components and calcium-based components are introduced into the red mud, and the red mud is strongly alkaline, so that more oxygen on the surface of the desulfurizing agent exists in a chemical adsorption oxygen form, and in the reaction process, the conversion from lattice oxygen to surface adsorption oxygen can occur, the desulfurization reaction is promoted, the high alkalinity of the red mud can maintain the alkaline environment of an alkaline solution, and the enriched active calcium-based components can be partially depolymerized under the action of the alkaline solution, so that the roughening of the calcium-based components in the calcium-silicon slag is promoted, and the desulfurization performance is improved; magnesium oxide as modifier as magnesium-based componentThe addition of the components can generate polyhalite which is stable at high temperature and is not easy to decompose with the sulfate which is a reaction product, thereby improving the stability of the desulfurizing agent, and the addition of the papermaking white mud can avoid SO after the silico-calcium slag is desulfurized and enters a pre-decomposing kiln 2 And can solve the problem of cement kiln crust caused by the desulfurization product as raw material entering the rotary kiln.
The invention also relates to a medium-temperature flue gas desulfurizing agent for the cement kiln, and in particular relates to the medium-temperature flue gas desulfurizing agent for the cement kiln, which is prepared by the preparation method.
The desulfurizer prepared by the method can be directly added into a dry cement production line in a raw material form, high-efficiency desulfurization is carried out in a medium-temperature section of a suspension preheater, desulfurization products enter a rotary kiln to participate in cement clinker generation, the quality of the clinker is not affected, and the calcium-silicon slag contains a large amount of dicalcium silicate, has similar components to cement clinker, and is beneficial to reutilization of the calcium-silicon slag.
The desulfurizer of the invention is added with a large amount of calcium-silicon slag, red mud and papermaking white mud in the preparation process, reduces the environmental pollution caused by industrial waste, changes waste into valuable, and has good economic benefit and environmental benefit.
Detailed Description
In order to characterize the technical effect of the invention, a medium-temperature flue gas desulfurizing agent is prepared and tested for desulfurizing effect.
In the test process, the desulfurizing agent is placed in a desulfurizing device to test the desulfurizing efficiency at different medium temperatures, and the unified dosage of the desulfurizing agent in the process is 0.5g/m 3 In the flue gas with SO as the component 2 Concentration 300ppm, O 2 The volume concentration is 1%, N 2 To equilibrate the gas, the test was performed in an atmosphere at a gas flow rate of 450 mL/min.
And (3) sintering the clinker by using a rotary kiln, introducing a desulfurizing agent into a third-stage suspension preheater, observing the skinning condition of the rotary kiln, grinding and preparing cement according to the mass ratio of clinker to gypsum to fly ash=85:5:10, and testing the mechanical strength of the cement.
Example 1
The medium-temperature flue gas desulfurizing agent comprises the following preparation steps: 1) Grinding and drying the calcium silicate slag and the red mud generated by magnesium smelting by a Pidgeon process according to the mass ratio of 1:0.25, uniformly mixing to ensure that the particle size is smaller than 150 mu m to obtain waste slag powder, 2) immersing the waste slag powder in a potassium hydroxide solution according to the solid-to-liquid ratio of 1:15, magnetically stirring, adjusting the solution to be neutral, adding MgO accounting for 7% of the mass of the waste slag powder and papermaking white mud accounting for 18% of the mass of the waste slag powder, continuously stirring, centrifugally washing, drying and grinding to obtain the magnesium silicate slag.
Through detection, the average desulfurization rate of 10min is 85% at 300 ℃, and the average desulfurization rate of 10min is 88% at 400 ℃; the cement 28d has a compressive strength of 49.5MPa in the rotary kiln without crust formation.
Example 2
The medium-temperature flue gas desulfurizing agent comprises the following preparation steps: 1) Grinding and drying the calcium silicate slag and the red mud generated by magnesium smelting by a Pidgeon process according to the mass ratio of 1:0.2, uniformly mixing to ensure that the particle size is smaller than 150 mu m to obtain waste slag powder, 2) immersing the waste slag powder in a potassium hydroxide solution according to the solid-to-liquid ratio of 1:20, magnetically stirring, adjusting the solution to be neutral, adding MgO accounting for 15% of the mass of the waste slag powder and papermaking white mud accounting for 12% of the mass of the waste slag powder, continuously stirring, centrifugally washing, drying and grinding to obtain the magnesium silicate slag.
Through detection, the average desulfurization rate of 10min is 89% at 300 ℃, and the average desulfurization rate of 10min is 96% at 400 ℃; the cement 28d has a compressive strength of 52.3MPa without crust in the rotary kiln.
Comparative example 1
The desulfurizing agent comprises the following preparation steps: 1) Grinding and drying the calcium silicate slag generated by the magnesium smelting by the Pidgeon process and the dust of a dust remover of a rotary kiln for the magnesium smelting by the Pidgeon process according to the mass ratio of 1:0.2:0.2, uniformly mixing the dust and the dolomite to ensure that the particle size of the dust is smaller than 150 mu m to obtain waste residue powder, 2) immersing the waste residue powder in a potassium hydroxide solution according to the solid-to-liquid ratio of 1:20, magnetically stirring the solution, adjusting the solution to be neutral, continuously stirring the solution, centrifugally washing, drying and grinding to obtain the magnesium alloy.
Through detection, the average desulfurization rate of 10min is 35% at 300 ℃, and the average desulfurization rate of 10min is 42% at 400 ℃; the skinning occurs when the cement 28d has a compressive strength of 46.5MPa when used in a rotary kiln.
Comparative example 2
The desulfurizing agent comprises the following preparation steps: 1) Grinding and drying the calcium silicate slag and the red mud generated by the magnesium smelting by the Pidgeon process according to the mass ratio of 1:0.2, uniformly mixing to ensure that the particle size is smaller than 150 mu m to obtain waste residue powder, 2) immersing the waste residue powder in a potassium hydroxide solution according to the solid-to-liquid ratio of 1:20, magnetically stirring, adjusting the solution to be neutral, continuously stirring, centrifugally washing, drying and grinding to obtain the magnesium alloy.
Through detection, the average desulfurization rate of 10min is 51% at 300 ℃, and the average desulfurization rate of 10min is 53% at 400 ℃; the skinning occurred when used in the rotary kiln, and the compressive strength of cement 28d was 47.6MPa.
Comparative example 3
The desulfurizing agent comprises the following preparation steps: 1) Grinding and drying the calcium silicate slag generated by magnesium smelting by the Pidgeon process, uniformly mixing the ground and dried calcium silicate slag to ensure that the grain diameter is less than 150 mu m to obtain waste slag powder, 2) immersing the waste slag powder in a potassium hydroxide solution according to a solid-to-liquid ratio of 1:20, magnetically stirring, then adjusting the solution to be neutral, adding MgO accounting for 15% of the mass of the waste slag powder and papermaking white mud accounting for 12% of the mass of the waste slag powder, continuously stirring, centrifugally washing, drying and grinding to obtain the magnesium silicate slag.
Through detection, the average desulfurization rate of 10min is 79% at 300 ℃, and the average desulfurization rate of 10min is 79% at 400 ℃; the cement 28d has a compressive strength of 43.6MPa in the rotary kiln without skinning.
Comparative example 4
The desulfurizing agent comprises the following preparation steps: 1) Grinding and drying the calcium silicate slag and the red mud generated by magnesium smelting by a Pidgeon process according to the mass ratio of 1:0.2, uniformly mixing to ensure that the particle size is smaller than 150 mu m to obtain waste slag powder, 2) immersing the waste slag powder in a potassium hydroxide solution according to the solid-to-liquid ratio of 1:20, magnetically stirring, adjusting the solution to be neutral, adding papermaking white mud accounting for 12% of the mass of the waste slag powder, continuously stirring, centrifugally washing, drying and grinding to obtain the magnesium silicate slag powder.
Through detection, the average desulfurization rate of 10min is 51% at 300 ℃, and the average desulfurization rate of 10min is 53% at 400 ℃; the cement 28d has a compressive strength of 44.8MPa in the rotary kiln without skinning.
Comparative example 5
The desulfurizing agent comprises the following preparation steps: 1) Grinding and drying the calcium silicate slag and the red mud generated by magnesium smelting by a Pidgeon process according to the mass ratio of 1:0.2, uniformly mixing to ensure that the particle size is smaller than 150 mu m to obtain waste slag powder, 2) immersing the waste slag powder in a potassium hydroxide solution according to the solid-to-liquid ratio of 1:20, magnetically stirring, adjusting the solution to be neutral, adding MgO accounting for 15% of the mass of the waste slag powder, continuously stirring, centrifugally washing, drying and grinding to obtain the magnesium silicate slag powder.
Through detection, the average desulfurization rate of 10min is 75% at 300 ℃, and the average desulfurization rate of 10min is 82% at 400 ℃; the skinning occurred when used in the rotary kiln, and the compressive strength of cement 28d was 44.5MPa.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limited thereto; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features can be replaced with equivalents; such modifications and substitutions do not depart from the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. The preparation method of the medium-temperature flue gas desulfurizing agent for the cement kiln is characterized by comprising the following steps of:
1) Grinding and drying the silicon-calcium slag and the red mud, uniformly mixing to ensure that the grain size is less than 150 mu m to obtain waste residue powder, wherein the silicon-calcium slag is calcium-silicon slag generated by smelting magnesium by a Pidgeon process,
2) Soaking the waste residue powder in an alkali solution, magnetically stirring, then regulating the solution to be neutral, adding MgO accounting for 5-15% of the mass of the waste residue powder and papermaking white mud accounting for 10-20% of the mass of the waste residue powder, continuously stirring, centrifugally washing, drying and grinding to obtain the composite material;
the mass ratio of the calcium silicate slag to the red mud in the step 1) is 1:0.2-0.3.
2. The method for preparing the medium-temperature flue gas desulfurization agent for the cement kiln according to claim 1, wherein the grinding in the step 1) adopts ball milling.
3. The method for preparing the medium-temperature flue gas desulfurizing agent for the cement kiln according to claim 1, wherein the alkaline solution in the step 2) is potassium hydroxide solution or sodium hydroxide solution, and the solid-to-liquid ratio of waste residue powder to the alkaline solution is 1:10-20.
4. The method for preparing the medium-temperature flue gas desulfurization agent for the cement kiln according to claim 1, wherein the magnetic stirring rotation speed in the step 2) is 300-500r/min, the magnetic stirring temperature is 70-80 ℃, and the magnetic stirring time is 1.5-2.5h.
5. The method for preparing a medium-temperature flue gas desulfurization agent in a cement kiln according to claim 1, wherein the stirring time in the step 2) is 1-2h.
6. The method for preparing the medium-temperature flue gas desulfurization agent for the cement kiln according to claim 1, wherein the drying temperature in the step 2) is 65-80 ℃ and the drying time is 8-10h.
7. The method for preparing a medium temperature flue gas desulfurization agent in a cement kiln according to claim 1, wherein the step 2) is carried out to a particle size of less than 75 μm.
8. The method for preparing the medium-temperature flue gas desulfurizer of the cement kiln according to claim 1, wherein the main chemical composition of the flue gas desulfurizer is CaO42-67 percent and SiO 2 19-28%、Fe 2 O 3 3-10%、MgO6-20%。
9. The medium-temperature flue gas desulfurizing agent for the cement kiln is characterized by being prepared by the preparation method of any one of claims 1-8.
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