WO2019062454A1 - 胶凝材料及其制造方法 - Google Patents

胶凝材料及其制造方法 Download PDF

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Publication number
WO2019062454A1
WO2019062454A1 PCT/CN2018/103036 CN2018103036W WO2019062454A1 WO 2019062454 A1 WO2019062454 A1 WO 2019062454A1 CN 2018103036 W CN2018103036 W CN 2018103036W WO 2019062454 A1 WO2019062454 A1 WO 2019062454A1
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Prior art keywords
metal oxide
flue gas
mno
weight
parts
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PCT/CN2018/103036
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English (en)
French (fr)
Inventor
童裳慧
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中晶环境科技股份有限公司
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Priority to JP2020517909A priority Critical patent/JP6963683B2/ja
Priority to US16/650,725 priority patent/US11339091B2/en
Publication of WO2019062454A1 publication Critical patent/WO2019062454A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B9/00—Magnesium cements or similar cements
    • C04B9/04—Magnesium cements containing sulfates, nitrates, phosphates or fluorides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • 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
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen 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
    • B01D53/81—Solid phase processes
    • B01D53/83—Solid phase processes with moving reactants
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/067—Slags
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/08—Slag cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • C04B28/105—Magnesium oxide or magnesium carbonate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • C04B28/346—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more phosphates
    • C04B28/348—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more phosphates the starting mixture also containing one or more reactive oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • 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
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal 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
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20723—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00008—Obtaining or using nanotechnology related materials

Definitions

  • the invention relates to a cementing material and a manufacturing method thereof, in particular to a gelling material produced by dry flue gas desulfurization and denitrification and a manufacturing method thereof.
  • Cement materials are extremely important in infrastructure construction and are important basic materials for China's development and modernization.
  • Enormous energy cement industry also generate a lot of byproducts pollute the environment, for example dust, CO 2, SO 2, NO X and wastewater.
  • pollutants are closely related to smog, photochemical smog, acid rain and other phenomena.
  • the processes of storage and transportation of raw materials, fuels, and cement products, as well as the processes of crushing, drying, grinding, and calcining of materials all generate a large amount of dust.
  • the calcination process of cement will produce a large amount of carbon disulfide and carbon dioxide, which will cause serious pollution to the environment.
  • the Chinese patent application with the application number 201510485072.4 discloses an integrated purification process for dry flue gas desulfurization, denitrification and dust removal.
  • the flue gas of the coal-fired boiler is firstly denitrated by the SNCR denitration system to enter the flue, and the flue gas is removed by the dust removal system.
  • Dust and then purify the secondary purification of the flue gas by spraying a dry powder absorbent into the flue.
  • the purified flue gas is filtered through the filtration system and discharged through the chimney.
  • the purification process is an integrated dry desulfurization, denitrification and dust removal purification process, the desulfurization rate is 95%, but the denitration efficiency is only about 75%, and the by-products are not fully utilized.
  • the Chinese patent application No. 201510304904.8 discloses a method for integrated treatment of flue gas.
  • An object of the present invention is to provide a method for producing a cementitious material, which can avoid excessive industrial wastewater generation, and can realize integrated treatment of flue gas desulfurization, denitrification and solid waste, and can obtain qualified cementing materials.
  • Another object of the present invention is to provide a cementitious material whose properties meet the requirements and make full use of industrial solid waste.
  • the invention provides a method for manufacturing a cemented material, comprising the following steps:
  • the flue gas absorbent comprises 10 to 23 parts by weight of nano metal oxide, 10 to 23 parts by weight of micron metal oxide and 40 ⁇ 60 parts by weight of magnesium oxide; wherein the nano metal oxide is selected from one or more of SiO 2 , CaO, Fe 2 O 3 , Al 2 O 3 , CuO, V 2 O 5 and MnO 2 , The micro metal oxide is selected from one or more of SiO 2 , CaO, Fe 2 O 3 , Al 2 O 3 , CuO, V 2 O 5 and MnO 2 ;
  • the by-product with magnesium oxide, industrial solid waste and additives to obtain the gelled material; wherein the industrial solid waste is selected from one or more of fly ash, slag powder and construction waste powder
  • the additive is selected from one or more of the group consisting of dihydrogen phosphate, monohydrogen phosphate, tartaric acid, tartrate or aminotrimethylenephosphonic acid.
  • the smoke absorbent is dry powder.
  • the sulfur dioxide content of the flue gas is 300 ⁇ 40000mg / Nm 3, the nitrogen oxide content of 50 ⁇ 600mg / Nm 3, oxygen
  • the content is 10 to 18 vol%
  • the flow rate is 2 to 5 m/s
  • the temperature is 110 to 200 °C.
  • the flue gas absorbent comprises 12 to 22 parts by weight of the nano metal oxide, 12 to 20 parts by weight of the micro metal oxide, and 42 to 60 parts by weight of the magnesium oxide.
  • the nano metal oxide comprises Fe 2 O 3 , V 2 O 5 and MnO 2 ; the micro metal oxide comprises Fe 2 O 3 , V 2 O 5 and MnO 2 .
  • the weight ratio of Fe 2 O 3 , V 2 O 5 and MnO 2 is from 3 to 5:3 to 8:5 to 10;
  • the weight ratio of Fe 2 O 3 , V 2 O 5 and MnO 2 in the micron metal oxide is from 3 to 5:3 to 8:5 to 10.
  • a weight ratio of Fe 2 O 3 , V 2 O 5 and MnO 2 is 4 to 5:5 to 6:6 to 7;
  • the weight ratio of Fe 2 O 3 , V 2 O 5 and MnO 2 in the micron metal oxide is 4 to 5:5 to 6:6 to 7.
  • the weight ratio of by-product to magnesium oxide, industrial solid waste and additives is from 100:50 to 200:50 to 150:3 to 15.
  • the industrial solid waste is selected from the group consisting of slag powder and fly ash in a weight ratio of 30 to 80:30 to 100.
  • the present invention also provides a gelling material which is obtained by any of the above methods.
  • the method of the invention effectively utilizes the industrial solid waste generated inside the enterprise under the condition of ensuring the normal flue gas desulfurization and denitrification of the enterprise, saves the material transfer transportation cost, and realizes turning waste into treasure.
  • Dry flue gas desulfurization and denitrification can avoid the production of a large amount of industrial waste liquid; at the same time, the main components of the obtained by-products are sulfate and nitrate, which can be fully utilized, and the cost of the cemented material can be greatly reduced.
  • the resulting cementitious material has a low cost and can directly replace the traditional 325#, 425#, 525# cement. According to the preferred technical solution of the present invention, problems such as low efficiency, low utilization value of by-product recycling, and even high price treatment of steel metallurgical enterprises and coal-fired power generation enterprises using conventional desulfurization and denitration technologies can be solved.
  • the method for producing a cementitious material of the present invention comprises (1) a desulfurization and denitration step; and (2) a mixing step. The details are described below.
  • the flue gas is subjected to dry desulfurization and denitration using a flue gas absorbent to form by-products. Flue gas desulfurization and denitrification can be carried out by using equipment conventional in the art, and will not be described herein.
  • the flue gas absorbent of the present invention comprises 10 to 23 parts by weight of the nano metal oxide, 10 to 23 parts by weight of the micron metal oxide, and 40 to 60 parts by weight of the magnesium oxide.
  • the nano metal oxide may be selected from one or more of SiO 2 , CaO, Fe 2 O 3 , Al 2 O 3 , CuO, V 2 O 5 , and MnO 2 .
  • the micron metal oxide may be selected from one or more of SiO 2 , CaO, Fe 2 O 3 , Al 2 O 3 , CuO, V 2 O 5 , and MnO 2 .
  • the flue gas absorbent may comprise from 12 to 22 parts by weight of the nanometal oxide, from 12 to 20 parts by weight of the micron metal oxide and from 42 to 60 parts by weight of the magnesium oxide. More preferably, the flue gas absorbent may comprise 15 to 22 parts by weight of the nano metal oxide, 15 to 20 parts by weight of the micron metal oxide, and 45 to 60 parts by weight of the magnesium oxide.
  • the nano metal oxide may have a particle diameter of 10 to 100 nm; preferably 20 to 90 nm.
  • the particle size of the micron metal oxide may be from 1 to 500 ⁇ m; preferably from 10 to 100 ⁇ m.
  • the nano metal oxide may be selected from one or more of CaO, Fe 2 O 3 , CuO, V 2 O 5 and MnO 2 , and the micro metal oxide is oxidized.
  • the substance is selected from one or more of CaO, Fe 2 O 3 , CuO, V 2 O 5 and MnO 2 .
  • the nano metal oxide preferably includes Fe 2 O 3 , V 2 O 5 and MnO 2 ;
  • the micro metal oxide preferably includes Fe 2 O 3 , V 2 O 5 and MnO 2 .
  • the weight ratio of Fe 2 O 3 , V 2 O 5 and MnO 2 is 3 to 5:3 to 8:5 to 10; In the micron metal oxide, the weight ratio of Fe 2 O 3 , V 2 O 5 and MnO 2 is from 3 to 5:3 to 8:5 to 10.
  • the SO 2 and NO in the flue gas reach the surface of the flue gas absorbent with the flue gas and are adsorbed by the surface; the nanometer and micron V 2 O 5 catalyze the conversion of SO 2 and O 2 into SO 3 in the flue gas.
  • Nano- and micro-scale Fe 2 O 3 and MnO 2 catalyze the conversion of NO and O 2 in the flue gas to NO 2 ; the catalytic oxidation of SO 3 and NO 2 and magnesium oxide and other adsorbents to form sulfate and nitrate; A small amount of unoxidized SO 2 , NO gas and an adsorbent such as magnesium oxide react to form sulfite and nitrite.
  • a weight ratio of Fe 2 O 3 , V 2 O 5 and MnO 2 is 4 to 5:5 to 6:6 to 7;
  • the weight ratio of Fe 2 O 3 , V 2 O 5 and MnO 2 is 4 to 5:5 to 6:6 to 7.
  • the flue gas absorbent comprises 60 parts by weight of magnesium oxide, 20.5 parts by weight of a nano metal oxide and 18.5 parts by weight of a micron metal oxide; among the nano metal oxides, Fe 2 O 3
  • the weight ratio of V 2 O 5 , MnO 2 and CaO is 4:5:6:190; in the micron metal oxide, the weight ratio of Fe 2 O 3 , V 2 O 5 , MnO 2 and CaO is 4:5:6:170.
  • the smoke absorbent may be in the form of a dry powder.
  • This absorbent is mixed with the flue gas, flue gas and further direct and SO 2 NO X removal, thereby completing the desulfurization of flue gas denitration process without the need for a large amount of water, and do not produce large amounts of industrial waste liquid.
  • the flue gas absorbent dry powder and the pre-dusting flue gas are thoroughly mixed in the flue gas pipeline, and then enter the absorption tower for desulfurization and denitration treatment, and the flue gas after desulfurization and denitration is discharged by the chimney.
  • the flue gas absorbent is used for dry flue gas desulfurization and denitrification.
  • the sulfur dioxide content of the flue gas may be 300 ⁇ 40000mg / Nm 3, preferably 500 ⁇ 30000mg / Nm 3, more preferably 600 ⁇ 5000mg / Nm 3.
  • the nitrogen oxide content may be 50 to 600 mg/Nm 3 , preferably 100 to 500 mg/Nm 3 , and more preferably 450 to 500 mg/Nm 3 .
  • the oxygen content may be 10 to 18 vol%, preferably 15 to 18 vol%.
  • the flow rate can be 2 to 5 m/s and the temperature is 110 to 200 °C.
  • the flue gas has a flow rate of 2.5 to 3.5 m/s and a temperature of 135 to 140 °C.
  • the above flue gas parameters all indicate the parameters at the flue gas inlet; the parameters at the flue gas outlet are determined according to the actual desulfurization and denitrification conditions.
  • the use of the above process parameters is advantageous for obtaining a by-product of stable quality, thereby facilitating stable production of the cementitious material.
  • the by-product is mixed with magnesium oxide, industrial solid waste and additives to obtain the gelled material.
  • by-products, magnesium oxide, industrial solid waste, and additives may each be pre-ground to 200 mesh or more, preferably 250 mesh or more, respectively, followed by mixing; by-products, magnesium oxide, industrial solid waste, and additives are mixed.
  • the mixture is uniformly obtained, and then the resulting mixture is ground to 200 mesh or more, preferably 250 mesh or more; or the ground by-product, magnesium oxide, industrial solid waste, and additives are mixed, and then further ground to obtain a gelled material.
  • the weight ratio of by-products to magnesium oxide, industrial solid waste, and additives is from 100:50 to 200:50 to 150:3 to 15.
  • they Preferably, they have a weight ratio of from 100:100 to 150:100 to 130:5 to 8. This fully guarantees the overall performance of the cementitious material.
  • the industrial solid waste may be selected from one or more of fly ash, slag powder or construction waste powder; preferably fly ash and/or slag powder.
  • the slag powder of the present invention include, but are not limited to, ball-milled slag, slag, steel slag or iron slag.
  • Fly ash is fine ash collected from the flue gas after coal combustion.
  • the fly ash is the main solid waste discharged from coal-fired power plants.
  • the slag is a slag discharged from iron making and steel making.
  • Construction waste powder is industrial solid waste that is pulverized from construction waste. The use of the above industrial solid waste is advantageous for obtaining a stable quality cementitious material.
  • the particle size of the industrial solid waste is preferably 200 mesh or more, more preferably 250 mesh or more.
  • the industrial solid waste is selected from the group consisting of slag powder and fly ash having a particle size of 200 mesh or more.
  • the additive is selected from one or more of dihydrogen phosphate, monohydrogen phosphate, tartaric acid, tartrate or aminotrimethylenephosphonic acid; preferably dihydrogen phosphate or monohydrogen phosphate .
  • dihydrogen phosphate or monohydrogen phosphate Specific examples include, but are not limited to, sodium dihydrogen phosphate or sodium monohydrogen phosphate.
  • the industrial solid waste is selected from the group consisting of slag powder and fly ash in a weight ratio of 30 to 80:30 to 100; preferably in a weight ratio of 40 to 70:40 to 90 a composition consisting of slag powder and fly ash.
  • the gelled material can be stably produced by the above method.
  • a cementitious material also called a "binder” refers to a material that can change from a slurry to a strong stone after physical and chemical action.
  • the cementitious material can bond other bulk or block materials to become a monolithic material with a certain mechanical strength.
  • the respective raw materials and their ratios are as described above and will not be described here.
  • by-products are obtained by dry desulfurization and denitrification of flue gas using a flue gas absorbent.
  • the flue gas absorbent and the dry desulfurization and denitration method are as described above.
  • the product of the present invention is preferably prepared by using a raw material having a weight ratio of 100:50 to 200:50 to 150:3 to 15, preferably 100:100 to 150:100 to 130:5.
  • a raw material having a weight ratio of 100:50 to 200:50 to 150:3 to 15, preferably 100:100 to 150:100 to 130:5.
  • the industrial solid waste is selected from the group consisting of slag powder and fly ash in a weight ratio of 30 to 80:30 to 100; preferably a composition composed of slag powder and fly ash in a weight ratio of 40 to 70:40 to 90 .
  • the compressive strength of the cemented material of the present invention after curing for 28 days may be 60-100 MPa, the bending strength is 10-20 MPa, and the water absorption rate is 3-10%; preferably, the compressive strength may be 66-80 MPa, bending The strength is 15 to 18 MPa, and the water absorption rate may be 5 to 8%.
  • the properties of the cementitious materials of the following examples were measured by GB/T50448-2008, and samples were prepared at a water-to-binder ratio of 0.35. Among them, the density and water absorption rate are the test results of curing 28d.
  • the raw materials listed in the table below were uniformly mixed to obtain a flue gas absorbent.
  • the nano-sized particle size was 20 nm; the micron-sized particle size was 10 ⁇ m.
  • the flue gas absorbent of Preparation Example 1 was used for dry flue gas desulfurization and denitrification.
  • the flow rate is 2.5 m/s and the oxygen content is 15 vol%; other parameters of the flue gas inlet and the parameters of the flue gas outlet are shown in Tables 2 and 3.
  • the by-product of 200 mesh or more is mixed with magnesium oxide, industrial solid waste of 200 mesh or more (fly ash, slag powder), and an additive (sodium dihydrogen phosphate) to obtain the gelled material.
  • Serial number project Quantity unit 1 Inlet smoke volume (working conditions) 1165000 m 3 /h 2 Standard smoke volume 779522 Nm 3 /h 3 Inlet temperature 135 °C 4 Sulfur dioxide inlet concentration 1600 Mg/Nm 3 5 Desulfurization efficiency 99.9 Wt% 6 Nitrogen oxide inlet concentration 450 Mg/Nm 3 7 Denitration efficiency 92 Wt% 8 Entrance smoke 111 Mg/Nm 3 9 Dust removal efficiency 99 Wt% 10 Flue gas moisture content 5.3 Wt%
  • Serial number project Quantity unit 1 Export smoke volume (working conditions) 116400 m 3 /h 2 exhaust temperature 65 °C 3 Sulfur dioxide emission concentration 1.70 Mg/Nm 3 4 NOx emission concentration 38.99 Mg/Nm 3 5 Export dust concentration 1.08 Mg/Nm 3 6 Output of by-products 4.32 t/h
  • Example 1 100 170 40 70 5
  • Example 2 100 170 70 40 5
  • Example 3 100 170 40 90 5
  • the flue gas absorbent of Preparation Example 1 was used for dry flue gas desulfurization and denitrification.
  • the flow rate was 2.5 m/s and the oxygen content was 15 vol%; the other parameters of the flue gas inlet and the parameters of the flue gas outlet are shown in Tables 6 and 7.
  • the by-product of 200 mesh or more is mixed with magnesium oxide, industrial solid waste of 200 mesh or more (fly ash, slag powder), and an additive (sodium dihydrogen phosphate) to obtain the gelled material.
  • Serial number project Quantity unit 1 Inlet smoke volume (working conditions) 1076050 m 3 /h 2 Standard smoke volume 711287 Nm 3 /h 3 Inlet temperature 140 °C 4 Sulfur dioxide inlet concentration 1650 Mg/Nm 3 5 Desulfurization efficiency 99.7 Wt% 6 Nitrogen oxide inlet concentration 500 Mg/Nm 3 7 Denitration efficiency 90 Wt% 8 Entrance smoke 105 Mg/Nm 3 9 Dust removal efficiency 99.3 Wt% 10 Flue gas moisture content 5.3 Wt%
  • Serial number project Quantity unit 1 Export smoke volume (working conditions) 810089 m 3 /h 2 exhaust temperature 68 °C 3 Sulfur dioxide emission concentration 6.57 Mg/Nm 3 4 NOx emission concentration 66.41 Mg/Nm 3 5 Export dust concentration 9.76 Mg/Nm 3 6 Output of by-products 4.31 t/h
  • Example 4 100 150 40 70 5
  • Example 5 100 150 70 40 5
  • Example 6 100 150 40 90 5
  • Examples 1 to 6 use the same kind of desulfurization and denitration agent. Although the working conditions are different, the desulfurization rate is above 99%, the denitration rate is above 90%, the dust removal rate is above 99%, and the obtained by-product composition is basically the same. The nature is stable. Reducing the amount of magnesium oxide will result in a decrease in mechanical properties.

Abstract

提供一种胶凝材料及其制造方法。该方法包括：(1)采用烟气吸收剂对烟气进行干法脱硫脱硝，从而形成副产物；烟气吸收剂包括10～23重量份纳米金属氧化物、10～23重量份微米金属氧化物和40～60重量份氧化镁；其中，纳米金属氧化物选自SiO2、CaO、Fe2O3、Al2O3、CuO、V2O5和MnO2中的一种或多种，微米金属氧化物选自SiO2、CaO、Fe2O3、Al2O3、CuO、V2O5和MnO2中的一种或多种；(2)将副产物与氧化镁、工业固体废物和添加剂混合均匀得到胶凝材料。该方法可以实现烟气脱硫脱硝、固体废物一体化治理，并获得合格的胶凝材料。

Description

胶凝材料及其制造方法 技术领域
本发明涉及一种胶凝材料及其制造方法，尤其是一种基于干法烟气脱硫脱硝生产的胶凝材料及其制造方法。
背景技术
水泥材料在基础设施建设中极为重要，是我国发展现代化的重要基础性材料。水泥工业的能耗巨大；同时还会产生很多污染环境的副产物，例如粉尘、CO 2、SO 2、NO X和废水等。这些污染物与雾霾、光化学烟雾、酸雨等现象密切相关。例如，原料、燃料、水泥成品的储运等工序，以及物料的破碎、烘干、粉磨和煅烧等工序，均产生大量粉尘。又如，水泥的煅烧过程将产生大量二硫化碳和二氧化碳，从而对环境造成严重污染。
此外，我国的镁法脱硫脱硝除尘后所得副产品的利用率还很低，副产品的再利用成为了环保行业中研究的热点问题。解决这一问题将对环保事业做出巨大贡献。副产品的再利用可以冲抵烟气脱硫脱硝的成本。申请号为201510485072.4的中国专利申请公开了一种干式烟气脱硫脱硝除尘一体化净化工艺，燃煤锅炉烟气先经SNCR脱硝系统实现初步脱硝后进入烟道，经除尘系统除去烟气中的粉尘，再通过向烟道内喷射干粉吸收剂来实现烟气的二次净化，净化后的烟气经过滤系统过滤后通过烟囱排放。该净化工艺为全干式脱硫、脱硝及除尘一体化净化工艺，脱硫率达到95％，但脱硝效率仅在75％左右，并且没有充分利用副产物。申请号为201510304904.8的中国专利申请公开了一种烟气一体化处理方法，借助湿法吸收脱硫设备，结合臭氧和过氧化氢协同氧化，实现了烟气同时脱硫脱硝脱汞除尘除雾综合治理。该 方法需要消耗大量工艺水，同时产生大量废水。在缺水地区，上述方法的应用将被限制。
发明内容
本发明的一个目的在于提供一种胶凝材料的生产方法，其可以避免产生过多的工业废水，并能够实现烟气脱硫脱硝、固废一体化治理，还可以获得合格的胶凝材料。
本发明的另一个目的在于提供一种胶凝材料，其性能满足要求，并且充分利用工业固体废物。
本发明提供一种胶凝材料的制造方法，包括如下步骤：
(1)采用烟气吸收剂对烟气进行干法脱硫脱硝，从而形成副产物；所述烟气吸收剂包括10～23重量份纳米金属氧化物、10～23重量份微米金属氧化物和40～60重量份氧化镁；其中，所述的纳米金属氧化物选自SiO 2、CaO、Fe 2O 3、Al 2O 3、CuO、V 2O 5和MnO 2中的一种或多种，所述的微米金属氧化物选自SiO 2、CaO、Fe 2O 3、Al 2O 3、CuO、V 2O 5和MnO 2中的一种或多种；
(2)将副产物与氧化镁、工业固体废物和添加剂混合均匀得到所述胶凝材料；其中，所述工业固体废物选自粉煤灰、矿渣粉、建筑垃圾粉中的一种或多种，所述添加剂选自磷酸二氢盐、磷酸一氢盐、酒石酸、酒石酸盐或氨基三亚甲基膦酸中的一种或多种。
根据本发明的方法，优选地，步骤(1)中，所述的烟气吸收剂为干粉状。
根据本发明的方法，优选地，在步骤(1)的干法脱硫脱硝过程中，所述烟气的二氧化硫含量为300～40000mg/Nm 3、氮氧化物含量为50～600mg/Nm 3、氧气含量为10～18vol％、流速为2～5m/s、且温度为110～200℃。
根据本发明的方法，优选地，步骤(1)中，所述烟气吸收剂包括12～22重量份纳米金属氧化物、12～20重量份微米金属氧化物和42～60重量份氧化镁。
根据本发明的方法，优选地，步骤(1)中，所述的纳米金属氧化物包括Fe 2O 3、V 2O 5和MnO 2；所述的微米金属氧化物包括Fe 2O 3、V 2O 5和MnO 2。
根据本发明的方法，优选地，在所述的纳米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为3～5:3～8:5～10；在所述的微米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为3～5:3～8:5～10。
根据本发明的方法，优选地，在所述的纳米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为4～5:5～6:6～7；在所述的微米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为4～5:5～6:6～7。
根据本发明的方法，优选地，步骤(2)中，副产物与氧化镁、工业固体废物和添加剂的重量比为100:50～200:50～150:3～15。
根据本发明的方法，优选地，步骤(2)中，所述工业固体废物选自重量比为30～80:30～100的矿渣粉和粉煤灰组成的组合物。
本发明还提供一种胶凝材料，该胶凝材料通过上述任一项方法制得。
本发明的方法在保证解决企业烟气正常脱硫脱硝的条件下，有效利用企业内部产生的工业固体废物，节约物料转移运输费用，实现变废为宝。干法烟气脱硫脱硝可以避免产生大量工业废液；同时，所得副产物的主要成份为硫酸盐和硝酸盐，将其充分利用，可以大幅降低胶凝材料的成本。所得胶凝材料成本很低，可以直接取代传统的325#、425#、525#水泥。根据本发明优选的技术方案，可以解决长期困扰钢铁冶金企业、燃煤发电企业采用传统脱硫脱硝技术效率低、副产物循 环利用价值较低、甚至需要高价处理等问题。
具体实施方式
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。
本发明的胶凝材料的制造方法包括(1)脱硫脱硝步骤；(2)混合步骤。下面进行详细介绍。
<脱硫脱硝步骤>
采用烟气吸收剂对烟气进行干法脱硫脱硝，从而形成副产物。可以采用本领域常规的设备进行烟气脱硫脱硝，这里不再赘述。本发明的所述烟气吸收剂包括10～23重量份纳米金属氧化物、10～23重量份微米金属氧化物和40～60重量份氧化镁。纳米金属氧化物可以选自SiO 2、CaO、Fe 2O 3、Al 2O 3、CuO、V 2O 5和MnO 2中的一种或多种。微米金属氧化物可以选自SiO 2、CaO、Fe 2O 3、Al 2O 3、CuO、V 2O 5和MnO 2中的一种或多种。优选地，烟气吸收剂可以包括12～22重量份纳米金属氧化物、12～20重量份微米金属氧化物和42～60重量份氧化镁。更优选地，烟气吸收剂可以包括15～22重量份纳米金属氧化物、15～20重量份微米金属氧化物和45～60重量份氧化镁。将烟气吸收剂的各个组分控制在上述范围，可以有效改善其脱硝效果，从而保证副产物的稳定性以及胶凝材料的稳定性。
在本发明的烟气吸收剂中，纳米金属氧化物的粒径可以在10～100nm；优选为20～90nm。微米金属氧化物的粒径可以在1～500μm；优选为10～100μm。采用上述不同粒径的金属氧化物与氧化镁组合，可以有效脱除烟气中的二氧化硫和氮氧化物，进而稳定地形成副产物，有利于胶凝材料的稳定生产。
在本发明的烟气吸收剂中，所述的纳米金属氧化物可以选自CaO、Fe 2O 3、CuO、V 2O 5和MnO 2中的一种或多种，所述的微米金属氧化物选自CaO、Fe 2O 3、CuO、V 2O 5和MnO 2中的一种或多种。例如，纳米金属氧化物优选包括Fe 2O 3、V 2O 5和MnO 2；微米金属氧化物优选包括Fe 2O 3、V 2O 5和MnO 2。根据本发明的一个实施方式，在所述的纳米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为3～5:3～8:5～10；在所述的微米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为3～5:3～8:5～10。
烟气中的SO 2和NO随烟气到达烟气吸收剂的表面，被其表面所吸附；纳米级和微米级的V 2O 5催化烟气中SO 2与O 2结合转化为SO 3，纳米级和微米级的Fe 2O 3和MnO 2催化烟气中NO与O 2结合转化为NO 2；催化氧化后的SO 3和NO 2和氧化镁等吸附剂作用生成硫酸盐和硝酸盐；少量未被氧化的SO 2、NO气体与氧化镁等吸附剂作用生成亚硫酸盐和亚硝酸盐。
根据本发明的一个实施方式，在所述的纳米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为4～5:5～6:6～7；在所述的微米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为4～5:5～6:6～7。
根据本发明的一个具体实施方式，烟气吸收剂包括60重量份氧化镁、20.5重量份纳米金属氧化物和18.5重量份微米金属氧化物；在所述的纳米金属氧化物中，Fe 2O 3、V 2O 5、MnO 2和CaO的重量比为4:5:6:190；在所述的微米金属氧化物中，Fe 2O 3、V 2O 5、MnO 2和CaO的重量比为4:5:6:170。
在本发明中，所述的烟气吸收剂可以为干粉状。这样可以直接将烟气吸收剂与烟气混合，进而对烟气进行SO 2和NO X的脱除，从而在不需要大量工艺水的情况下完成烟气的脱硫脱硝，并且不产生大量工业废液。例如，将烟气吸收剂干粉与预除尘后的烟气在烟气管道充 分混合，然后进入吸收塔进行脱硫脱硝处理，脱硫脱硝后的烟气由烟囱排出。
采用上述烟气吸收剂进行干法烟气脱硫脱硝。在干法脱硫脱硝过程中，所述烟气的二氧化硫含量可以为300～40000mg/Nm 3、优选为500～30000mg/Nm 3、更优选为600～5000mg/Nm 3。氮氧化物含量可以为50～600mg/Nm 3、优选为100～500mg/Nm 3、更优选为450～500mg/Nm 3。氧气含量可以为10～18vol％、优选为15～18vol％。流速可以为2～5m/s、且温度为110～200℃。优选地，所述烟气的流速为2.5～3.5m/s、且温度为135～140℃。上述烟气参数均表示烟气入口处的参数；烟气出口处的参数根据实际脱硫脱硝情况而定。采用上述工艺参数，有利于获得质量稳定的副产物，从而有利于胶凝材料的稳定生产。
<混合步骤>
将副产物与氧化镁、工业固体废物和添加剂混合均匀得到所述胶凝材料。在本发明中，可以将副产物、氧化镁、工业固体废物和添加剂均分别预先研磨至200目以上，优选为250目以上，然后进行混合；将副产物、氧化镁、工业固体废物和添加剂混合均匀得到混合物，然后将所得混合物研磨至200目以上，优选为250目以上；或者将研磨后的副产物、氧化镁、工业固体废物和添加剂混合，然后进一步研磨得到胶凝材料。
在本发明中，副产物与氧化镁、工业固体废物和添加剂的重量比为100:50～200:50～150:3～15。优选地，它们的重量比为100:100～150:100～130:5～8。这样可以充分保证胶凝材料的综合性能。
在本发明中，所述工业固体废物可以选自粉煤灰、矿渣粉或建筑垃圾粉中的一种或多种；优选为粉煤灰和/或矿渣粉。本发明的矿渣粉 的实例包括但不限于经球磨后的炉渣、矿渣、钢渣或铁渣。粉煤灰是从煤燃烧后的烟气中收捕下来的细灰，粉煤灰是燃煤电厂排出的主要固体废物。矿渣是炼铁、炼钢排出的渣料。建筑垃圾粉是以建筑垃圾为原料，粉碎而成的工业固体废物。采用上述工业固体废物，有利于获得质量稳定的胶凝材料。工业固体废物的粒度最好在200目以上，更优选为250目以上。根据本发明的一个实施方式，所述工业固体废物选自粒度在200目以上的矿渣粉和粉煤灰。
在本发明中，所述添加剂选自磷酸二氢盐、磷酸一氢盐、酒石酸、酒石酸盐或氨基三亚甲基膦酸中的一种或多种；优选为磷酸二氢盐或磷酸一氢盐。具体的实例包括但不限于磷酸二氢钠或磷酸一氢钠。采用上述添加剂，可以充分保证胶凝材料的综合性能。
根据本发明的一个实施方式，所述工业固体废物选自重量比为30～80:30～100的矿渣粉和粉煤灰组成的组合物；优选为重量比为40～70:40～90的矿渣粉和粉煤灰组成的组合物。
<胶凝材料>
采用上述方法可以稳定地生产胶凝材料。胶凝材料也称之为“胶结料”，是指经物理、化学作用后，能从浆体变成坚固的石状体的材料。胶凝材料可以胶结其他散粒或块状的物料，从而成为具有一定机械强度的整体材料。各个原料及其配比如前所述，这里不再赘述。在这些原料中，副产物为采用烟气吸收剂对烟气进行干法脱硫脱硝获得的。烟气吸收剂以及干法脱硫脱硝方法如前所述。
为了改善制品综合性能，本发明的制品优选采用如下配比的原料制成：重量比为100:50～200:50～150:3～15、优选为100:100～150:100～130:5～8的副产物与氧化镁、工业固体废物和添加剂。工业固体废物选自重量比为30～80:30～100的矿渣粉和粉煤灰组成的组 合物；优选为重量比为40～70:40～90的矿渣粉和粉煤灰组成的组合物。
本发明的胶凝材料在养护28d后的抗压强度可以为60～100MPa、弯折强度为10～20MPa、吸水率为3～10％；优选地，抗压强度可以为66～80MPa、弯折强度为15～18MPa、吸水率可以为5～8％。
以下制备例和实施例中的“份”表示重量份，除非特别声明。
以下实施例的胶凝材料的性能采用GB/T50448-2008进行测定，按照水胶比为0.35制备试样。其中，密度和吸水率均为养护28d的测试结果。
制备例1
将下表所列的原料混合均匀，获得烟气吸收剂。纳米级的粒径为20nm；微米级的粒径为10μm。
表1、烟气吸收剂的配方
Figure PCTCN2018103036-appb-000001
实施例1～3
(1)采用制备例1的烟气吸收剂进行烟气干法脱硫脱硝。流速为2.5m/s，氧气含量为15vol％；烟气入口的其他参数、烟气出口的参数如表2和3所示。
(2)将200目以上的副产物与氧化镁、200目以上的工业固体废物(粉煤灰、矿渣粉)和添加剂(磷酸二氢钠)混合均匀得到所述胶凝材料。
表2、烟气脱硫脱硝项目工况参数
序号 项目 数量 单位
1 入口烟气量(工况) 1165000 m 3/h
2 标态烟气量 779522 Nm 3/h
3 入口温度 135 ℃
4 二氧化硫入口浓度 1600 mg/Nm 3
5 脱硫效率 99.9 wt％
6 氮氧化物入口浓度 450 mg/Nm 3
7 脱硝效率 92 wt％
8 入口烟尘 111 mg/Nm 3
9 除尘效率 99 wt％
10 烟气含湿量 5.3 wt％
表3、脱硫脱硝项目排放情况
序号 项目 数量 单位
1 出口烟气量(工况) 116400 m 3/h
2 排烟温度 65 ℃
3 二氧化硫排放浓度 1.70 mg/Nm 3
4 氮氧化物排放浓度 38.99 mg/Nm 3
5 出口粉尘浓度 1.08 mg/Nm 3
6 副产物的产出量 4.32 t/h
胶凝材料的物料配比和性能测试结果参见表4和表5。
表4、胶凝材料的物料配比
编号 副产物 氧化镁 矿渣 粉煤灰 添加剂
实施例1 100 170 40 70 5
实施例2 100 170 70 40 5
实施例3 100 170 40 90 5
表5、胶凝材料的性能测试结果
Figure PCTCN2018103036-appb-000002
实施例4～6
(1)采用制备例1的烟气吸收剂进行烟气干法脱硫脱硝。流速为2.5m/s，氧气含量为15vol％；烟气入口的其他参数、烟气出口的参数如表6和7所示。
(2)将200目以上的副产物与氧化镁、200目以上的工业固体废物(粉煤灰、矿渣粉)和添加剂(磷酸二氢钠)混合均匀得到所述胶凝材料。
表6、烟气脱硫脱硝项目工况参数
序号 项目 数量 单位
1 入口烟气量(工况) 1076050 m 3/h
2 标态烟气量 711287 Nm 3/h
3 入口温度 140 ℃
4 二氧化硫入口浓度 1650 mg/Nm 3
5 脱硫效率 99.7 wt％
6 氮氧化物入口浓度 500 mg/Nm 3
7 脱硝效率 90 wt％
8 入口烟尘 105 mg/Nm 3
9 除尘效率 99.3 wt％
10 烟气含湿量 5.3 wt％
表7、脱硫脱硝项目排放情况
序号 项目 数量 单位
1 出口烟气量(工况) 810089 m 3/h
2 排烟温度 68 ℃
3 二氧化硫排放浓度 6.57 mg/Nm 3
4 氮氧化物排放浓度 66.41 mg/Nm 3
5 出口粉尘浓度 9.76 mg/Nm 3
6 副产物的产出量 4.31 t/h
胶凝材料物料配比和性能测试结果参见表8和表9。
表8、胶凝材料物料配比
编号 副产物 氧化镁 矿渣 粉煤灰 添加剂
实施例4 100 150 40 70 5
实施例5 100 150 70 40 5
实施例6 100 150 40 90 5
表9、胶凝材料性能测试结果
Figure PCTCN2018103036-appb-000003
实施例1～6采用同种脱硫脱硝剂，虽然工况不同，但是脱硫率均在99％以上，脱硝率在90％以上，除尘率在99％以上，所得副产物组成基本一致，胶凝材料性质稳定。减少氧化镁用量，会导致力学性能有所下降。
本发明并不限于上述实施方式，在不背离本发明的实质内容的情 况下，本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。

Claims (10)

  1. 一种胶凝材料的制造方法，其特征在于，包括如下步骤：
    (1)采用烟气吸收剂对烟气进行干法脱硫脱硝，从而形成副产物；所述烟气吸收剂包括10～23重量份纳米金属氧化物、10～23重量份微米金属氧化物和40～60重量份氧化镁；其中，所述的纳米金属氧化物选自SiO 2、CaO、Fe 2O 3、Al 2O 3、CuO、V 2O 5和MnO 2中的一种或多种，所述的微米金属氧化物选自SiO 2、CaO、Fe 2O 3、Al 2O 3、CuO、V 2O 5和MnO 2中的一种或多种；
    (2)将副产物与氧化镁、工业固体废物和添加剂混合均匀得到所述胶凝材料；其中，所述工业固体废物选自粉煤灰、矿渣粉、建筑垃圾粉中的一种或多种，所述添加剂选自磷酸二氢盐、磷酸一氢盐、酒石酸、酒石酸盐或氨基三亚甲基膦酸中的一种或多种。
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述的烟气吸收剂为干粉状。
  3. 根据权利要求1所述的方法，其特征在于，在步骤(1)的干法脱硫脱硝过程中，所述烟气的二氧化硫含量为300～40000mg/Nm 3、氮氧化物含量为50～600mg/Nm 3、氧气含量为10～18vol％、流速为2～5m/s、且温度为110～200℃。
  4. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述烟气吸收剂包括12～20重量份纳米金属氧化物、12～20重量份微米金属氧化物和42～60重量份氧化镁。
  5. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述的纳米金属氧化物包括Fe 2O 3、V 2O 5和MnO 2；所述的微米金属氧化物包括Fe 2O 3、V 2O 5和MnO 2。
  6. 根据权利要求5所述的方法，其特征在于，在所述的纳米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为3～5:3～8:5～10；在所 述的微米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为3～5:3～8:5～10。
  7. 根据权利要求5所述的方法，其特征在于，在所述的纳米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为4～5:5～6:6～7；在所述的微米金属氧化物中，Fe 2O 3、V 2O 5和MnO 2的重量比为4～5:5～6:6～7。
  8. 根据权利要求1～7任一项所述的方法，其特征在于，步骤(2)中，副产物与氧化镁、工业固体废物和添加剂的重量比为100:50～200:50～150:3～15。
  9. 根据权利要求8所述的方法，其特征在于，步骤(2)中，所述工业固体废物选自重量比为30～80:30～100的矿渣粉和粉煤灰组成的组合物。
  10. 一种胶凝材料，其特征在于，该胶凝材料通过权利要求1～9任一项所述的方法制得。
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