CN116510495B - Sintering flue gas desulfurizing agent and preparation method thereof - Google Patents
Sintering flue gas desulfurizing agent and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 84
- 239000003546 flue gas Substances 0.000 title claims abstract description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000005245 sintering Methods 0.000 title claims abstract description 15
- 230000003009 desulfurizing effect Effects 0.000 title claims description 38
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 35
- 230000023556 desulfurization Effects 0.000 claims abstract description 35
- 239000002699 waste material Substances 0.000 claims abstract description 24
- 239000002028 Biomass Substances 0.000 claims abstract description 22
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 18
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 18
- 239000004571 lime Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 238000000855 fermentation Methods 0.000 claims description 12
- 230000004151 fermentation Effects 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- 239000012778 molding material Substances 0.000 claims description 10
- 239000008107 starch Substances 0.000 claims description 10
- 235000019698 starch Nutrition 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000002550 fecal effect Effects 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 244000038280 herbivores Species 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000000813 microbial effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 241000283690 Bos taurus Species 0.000 claims description 2
- 241000283074 Equus asinus Species 0.000 claims description 2
- 241000283073 Equus caballus Species 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 235000010269 sulphur dioxide Nutrition 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect 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
- 239000003245 coal Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/346—Controlling the process
-
- 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
- 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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- 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
- B01D53/86—Catalytic processes
- B01D53/88—Handling or mounting catalysts
- B01D53/885—Devices in general for catalytic purification of waste gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/38—Stirring or kneading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- 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
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to the technical field of flue gas desulfurization, in particular to a sintering flue gas desulfurization agent and a preparation method thereof, and discloses the sintering flue gas desulfurization agent which comprises the following raw materials in parts by weight: 100-800 parts of lime waste residue, 200-500 parts of binder, 2-25 parts of catalytic component, 30-120 parts of pore-forming agent and 50-150 parts of biomass water-retaining agent.
Description
Technical Field
The invention relates to the technical field of flue gas desulfurization, in particular to a sintering flue gas desulfurizing agent and a preparation method thereof.
Background
Since fossil fuels such as coal are burned to produce harmful gases such as sulfur dioxide, flue gas desulfurization technology has become an important focus in industrial fields such as coal mines and power plants. The flue gas desulfurization mainly adopts two methods of wet desulfurization and dry desulfurization. The wet desulfurization is to absorb sulfur dioxide by using aqueous solution to form sulfate ions so as to achieve the purpose of desulfurization. However, the chemical reagent used in the method needs to be purified and treated, so that the pollution to the environment is aggravated; meanwhile, a large amount of wastewater is generated in the water treatment process, and recovery treatment is needed. Dry desulfurization refers to the absorption of sulfur dioxide in flue gas by the addition of dry materials to the flue gas, such as calcium-based or sodium-based absorbents. In this way, the sulphur dioxide in the flue gas is converted into solid waste such as calcium sulphate or sodium sulphate, which waste needs to be treated and recycled. In the dry desulfurization process, a sintering flue gas desulfurization agent is widely used. The desulfurizing agent is formed by mixing various materials, such as calcium oxide, calcium hydroxide, sodium bicarbonate and the like. The materials can absorb sulfur dioxide in flue gas and have higher catalytic activity, so the materials are widely used in the sintering flue gas desulfurization process.
In the prior art, as in CN 111330424B, a flue gas desulfurizing agent is reported, but the defect of poor crushing resistance of the calcium-based desulfurizing agent in the prior art is not completely overcome; as another example, CN 102698575B reports a desulfurizing agent and a preparation method thereof, which uses slag tail mud and lime kiln dust as raw materials, and although the structural strength is improved, the overall desulfurizing efficiency is reduced due to the reduction of the porosity.
Disclosure of Invention
Aiming at the prior art, the invention provides a sintering flue gas desulfurizing agent and a preparation method thereof, which are used for preparing the sintering flue gas desulfurizing agent by using industrial and agricultural wastes such as lime waste residues, expired starch and livestock manure in a large amount as production raw materials and mixing the raw materials after treatment, so as to solve the problems of low structural strength, low porosity, poor desulfurizing performance, high use cost, difficult waste treatment and the like of the desulfurizing agent.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a sintering flue gas desulfurizing agent, which comprises the following raw materials in parts by weight: 100-800 parts of lime waste residue, 200-500 parts of binder, 2-25 parts of catalytic component, 30-120 parts of pore-forming agent and 50-150 parts of biomass water-retaining agent.
Further, the binder is one or more of kaolin, diatomite, bentonite and attapulgite.
Further, the active component is one or more of ferric oxide, manganese dioxide, cobaltosic oxide and cerium oxide.
Further, the pore-forming agent is one or more of expired starch and ammonium bicarbonate.
Further, the biomass water-retaining agent is prepared by the following method: mechanically dehydrating the fecal raw material from herbivores until the moisture content is lower than 10wt%, crushing the dehydrated fecal raw material to form biomass powder, steaming the crushed biomass powder for 2-4 hours, cooling the solid obtained by filtration to room temperature, adding a fermenting agent, uniformly stirring in a fermentation tank for fermentation, and drying the fermented product; the fermenting agent is a microbial fermenting agent, the adding amount is 0.001-1% of the total mass of the fermented product, the fermentation temperature is 15-30 ℃, and the fermentation time is 2-7 days;
the bonding agent promotes the combination of the components and improves the structural strength. The catalytic active sites are uniformly dispersed in the oxide, so that dissociation and activation of oxygen and generation of active oxygen in the desulfurization process are accelerated, and reaction absorption is promoted. Proper amount of biomass water-retaining agent is added to ensure the supersaturation degree required by the growth of calcium hydroxide crystals, promote the growth of the crystals into hexagonal thin planes, and the formed slaked lime surface has rich pores formed by mutually staggered layers; and the addition of a proper amount of pore-forming agent can increase the included angle between calcium hydroxide crystal layers, so that the pore diameter of the pore is further enlarged, and a large number of capillary pores are formed. The invention adopts hydrothermal reaction to lead calcium and silicon to generate the calcium silicate composite oxide, the composite oxide has fibrous structure, increases the porosity of the desulfurizing agent, improves the specific surface area of the desulfurizing agent, and reduces the generation of CaSO 4 Blocking the pore canal of the desulfurizing agent, and improving the utilization rate of the desulfurizing agent;
further, the herbivore is one or more of cow, horse and donkey.
In a second aspect of the present invention, there is provided a method of preparing a sintering flue gas desulfurization agent, comprising the steps of:
(1) Crushing lime waste residues, and ball-milling to obtain a particle size of 200 meshes;
(2) Uniformly mixing the crushed lime waste residue, the binder, the catalytic component, the pore-forming agent and the biomass water-retaining agent;
(3) Mixing water with the mixture obtained in step (2) at a ratio of 1: mixing the materials in the mass ratio of (1-10), stirring, extruding, forming and cutting to obtain a formed material; the diameter of the molding material is 1 mm-10 mm, and the cutting length is 5 mm-20 mm;
(4) Calcining the molding material at 400-900 ℃ for 4-6 h, and naturally cooling to normal temperature.
In a third aspect of the invention, there is provided the use of a sintered flue gas desulfurization agent in flue gas desulfurization.
Further, the process conditions are as follows: the volume fraction of oxygen is 2-10%, and the inlet SO 2 The concentration is 500-2500mg/m 3 The reaction temperature is 250-550 ℃, and the reaction space velocity is 500-5000h -1 。
The invention has the beneficial effects that:
(1) The invention improves the radial crushing strength of the material, and is more beneficial to keeping the structural integrity under long-term high-speed smoke impact;
(2) The invention further improves the porosity of the material, increases the retention time of the sulfur-containing waste gas in the desulfurizing agent, prolongs the reaction process of the sulfur in the waste gas and the desulfurizing agent, and improves the desulfurizing efficiency.
(3) The desulfurizing agent prepared by the invention is derived from various wastes, including industrial wastes and animal husbandry wastes, provides a treatment method for the various wastes, and reduces unordered discharge of the wastes.
(4) The invention changes waste into valuable through the treatment process, provides a high-efficiency desulfurizing agent for waste gas treatment industries such as power plants and the like, and reduces the use cost of the desulfurizing agent for enterprises due to low price of raw materials.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention, which are not specifically described, are all conventional in the art and are commercially available.
The biomass water-retaining agent used in the invention is prepared by the following method: mechanically dehydrating fecal raw materials from herbivores until the moisture content is lower than 10wt%, crushing the dehydrated fecal raw materials to form biomass powder, steaming the crushed biomass powder for 4 hours, cooling solid matters obtained by filtering to room temperature, adding a fermenting agent, uniformly stirring in a fermentation tank for fermentation, and drying a fermented product; the starter (purchased from Shandong Jundy biotechnology Co., ltd., organic material starter) is a microbial starter, the addition amount is 0.1% of the total mass of the fermented product, the ambient temperature during fermentation is 25 ℃, and the fermentation time is 7 days.
Example 1: preparation of desulfurizing agent 1
1. The raw materials comprise:
lime waste residue (100 parts), kaolin (200 parts), mnO 2 (2 parts), expired starch (30 parts) and biomass water-retaining agent (50 parts).
2. The preparation method comprises the following steps:
(1) Crushing lime waste residues, and ball-milling to obtain a particle size of 200 meshes;
(2) Crushed lime waste residue, kaolin as binder and MnO as catalytic component 2 The expired starch serving as the pore-forming agent and the biomass water-retaining agent are uniformly mixed;
(3) Mixing water with the mixture obtained in step (2) at a ratio of 1: mixing, stirring, extruding, forming and cutting according to the mass ratio of 10 to obtain a formed material; the diameter of the molding material is 5mm, and the cutting length is 20mm;
(4) Calcining the molding material at 800 ℃ for 4 hours, and naturally cooling to normal temperature.
Example 2: preparation of desulfurizing agent 2
1. The raw materials comprise:
lime waste residue (800 parts), kaolin (500 parts), mnO 2 (25 parts), expired starch (120 parts) and biomass water-retaining agent (150 parts).
2. The preparation method comprises the following steps:
(1) Crushing lime waste residues, and ball-milling to obtain a particle size of 200 meshes;
(2) Crushed lime waste residue, kaolin as binder and MnO as catalytic component 2 The expired starch serving as the pore-forming agent and the biomass water-retaining agent are uniformly mixed;
(3) Mixing water with the mixture obtained in step (2) at a ratio of 1: mixing, stirring, extruding, forming and cutting according to the mass ratio of 10 to obtain a formed material; the diameter of the molding material is 5mm, and the cutting length is 20mm;
(4) Calcining the molding material at 800 ℃ for 4 hours, and naturally cooling to normal temperature.
Example 3: preparation of desulfurizing agent 3
1. The raw materials comprise:
lime waste residue (580 parts), kaolin (300 parts), mnO 2 (17 parts), expired starch (61 parts) and biomass water-retaining agent (109 parts).
2. The preparation method comprises the following steps:
(1) Crushing lime waste residues, and ball-milling to obtain a particle size of 200 meshes;
(2) Crushed lime waste residue, kaolin as binder and MnO as catalytic component 2 The expired starch serving as the pore-forming agent and the biomass water-retaining agent are uniformly mixed;
(3) Mixing water with the mixture obtained in step (2) at a ratio of 1: mixing, stirring, extruding, forming and cutting according to the mass ratio of 10 to obtain a formed material; the diameter of the molding material is 5mm, and the cutting length is 20mm;
(4) Calcining the molding material at 800 ℃ for 4 hours, and naturally cooling to normal temperature.
Comparative example 1: preparation of desulfurizing agent 4
A sintered flue gas desulfurization agent differs from example 3 only in that a binder is not used in the preparation of the desulfurization agent 4.
Comparative example 2: preparation of desulfurizing agent 5
A sintered flue gas desulfurization agent differs from example 3 only in that no pore-forming agent is used in the preparation of the desulfurization agent 5.
Comparative example 3: preparation of desulfurizing agent 6
The sintering flue gas desulfurization agent differs from example 3 only in that a biomass water-retaining agent is not used in the preparation process of the desulfurization agent 6.
Comparative example 4: preparation of desulfurizing agent 7
The sintering flue gas desulfurization agent differs from example 3 only in that a binder, a pore-forming agent and a water-retaining agent are not used in the preparation process of the desulfurization agent 7.
The detection method of each index related by the invention comprises the following steps:
(1) The method for detecting the radial crush strength refers to: determination of crushing resistance of HG/T2782-2011 fertilizer catalyst particles;
(2) The porosity was calculated as follows:
P＝(V 0 -V)/V 0 ×100％＝(1-ρ 0 /ρ)×100％
p-material porosity (%);
V 0 the volume of the material in its natural state, or apparent volume, cm 3 Or m 3 ；ρ 0 G/cm, the bulk density of the material 3 Or kg/m 3 ；
V-absolute compact volume of material, cm 3 Or m 3 The method comprises the steps of carrying out a first treatment on the surface of the ρ is the density of the material, g/cm 3 Or kg/m 3 ；
(3) SO in flue gas 2 The concentration adopts a flue gas analyzer to detect the inlet and outlet gas concentration once per hour, the detection data of 48 hours are taken to calculate the average value, and the SO of the flue gas is introduced in the testing method 2 The concentration is 2000ppm, and the contact time of the flue gas and the flue gas desulfurizing agent is 6.0s. Analysis of sample SO with Thermo ICS-5000 ion chromatography System 2 The analytical column was Thermo AS11-HC,4x250mm (P/N082313), the guard column was: thermo AS11-HC,4x250mm (P/N078034), SO in the exhaust 2 When the content exceeds 50ppm, the desulfurizing agent is considered to have penetrated, and the penetration time, the penetration sulfur capacity (penetration sulfur capacity is the content of elemental sulfur in the desulfurizing agent) and the desulfurization rate up to the penetration time are calculated.
The calculation method of desulfurization efficiency is as follows:
desulfurization effectRate= (C 0 -C)/C 0 ×100％
C 0 SO before flue gas passes through desulfurizing agent 2 Concentration in ppm or mg/Nm 3 ；
SO after C-flue gas passes through desulfurizing agent 2 Concentration in ppm or mg/Nm 3 ；
The results are shown in Table 1.
Table 1: flue gas desulfurizing agent performance index detection result
As can be seen from the detection data of examples 1-3, example 3 is the optimal example, and the flue gas desulfurization agent provided by the invention has larger porosity (53%), higher radial crushing strength (301N/cm), higher penetrating sulfur capacity (calculated as elemental sulfur) (16.2), longer penetrating time (39 h) and higher desulfurization efficiency (98%). Comparing with comparative examples 1 to 4, it is found that the product with excellent performance can be obtained only by feeding the materials in proper proportion according to the specified raw material composition, and the full performance of the desulfurizing agent is ensured.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (5)
1. The sintering flue gas desulfurizing agent is characterized by comprising the following raw materials in parts by weight: 580 parts of lime waste residue, 300 parts of kaolin, 17 parts of manganese dioxide, 61 parts of expired starch and 109 parts of biomass water-retaining agent;
the biomass water-retaining agent is prepared by the following method: mechanically dehydrating fecal raw materials from herbivores until the moisture content is lower than 10wt%, crushing the dehydrated fecal raw materials to form biomass powder, steaming the crushed biomass powder for 4 hours, cooling solid matters obtained by filtering to room temperature, adding a fermenting agent, uniformly stirring in a fermentation tank for fermentation, and drying a fermented product; the starter is a microbial starter, the addition amount of the starter is 0.1% of the total mass of the fermented product, the fermentation temperature is 25 ℃, and the fermentation time is 7 days.
2. The sintered flue gas desulfurization agent of claim 1, wherein the herbivore is one or more of bovine, equine, and donkey.
3. The method for preparing a sintering flue gas desulfurization agent according to any one of claims 1 to 2, comprising the steps of:
(1) Crushing lime waste residues, and ball-milling to obtain a particle size of 200 meshes;
(2) Uniformly mixing the crushed lime waste residue, kaolin, manganese dioxide, expired starch and a biomass water retention agent;
(3) Mixing water with the mixture obtained in step (2) at a ratio of 1: mixing, stirring, extruding, forming and cutting according to the mass ratio of 10 to obtain a formed material; the diameter of the molding material is 5mm, and the cutting length is 20mm;
(4) Calcining the molding material at 800 ℃ for 4 hours, and naturally cooling to normal temperature.
4. Use of a sintered flue gas desulfurization agent according to any one of claims 1-2 for flue gas desulfurization.
5. The use according to claim 4, wherein the process conditions are: the volume fraction of oxygen is 2-10%, and the inlet SO 2 The concentration is 500-2500mg/m 3 The reaction temperature is 250-550 ℃, and the reaction space velocity is 500-5000h -1 。
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