CN113666679A - Method for producing building material by using desulfurization and denitrification byproducts - Google Patents

Method for producing building material by using desulfurization and denitrification byproducts Download PDF

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Publication number
CN113666679A
CN113666679A CN202110993452.4A CN202110993452A CN113666679A CN 113666679 A CN113666679 A CN 113666679A CN 202110993452 A CN202110993452 A CN 202110993452A CN 113666679 A CN113666679 A CN 113666679A
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parts
weight
desulfurization
denitrification
building
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王春霞
张焜
魏闯
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Environment Sustainable System Engineering Technology Co ltd
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Environment Sustainable System Engineering Technology Co ltd
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Priority to CN202110993452.4A priority Critical patent/CN113666679A/en
Publication of CN113666679A publication Critical patent/CN113666679A/en
Priority to PCT/CN2021/143498 priority patent/WO2023024392A1/en
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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
    • 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
    • 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
    • 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
    • B01D53/54—Nitrogen compounds
    • B01D53/56—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
    • 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
    • C04B18/021—Agglomerated materials, e.g. artificial aggregates agglomerated by a mineral binder, e.g. cement
    • 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
    • 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
    • C04B2111/00017—Aspects relating to the protection of the environment
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a method for producing building materials by using desulfurization and denitrification byproducts. The method comprises the following steps: s1, mixing raw materials including 4-16 parts by weight of iron powder, 1-14 parts by weight of bentonite, 2-20 parts by weight of cement, 20-70 parts by weight of lime powder, 2-14 parts by weight of manganese ore, 4-10 parts by weight of cerium ore, 2-15 parts by weight of cobalt ore and 2-15 parts by weight of pore-forming agent, granulating and drying to obtain a desulfurization and denitrification absorbent; s2, placing the desulfurization and denitrification absorbent in a flue gas environment for desulfurization and denitrification to obtain a desulfurization and denitrification byproduct; and S3, producing the building material by using the desulfurization and denitrification byproducts. The method not only can effectively realize desulfurization and denitrification, but also can realize resource recycling of desulfurization and denitrification byproducts.

Description

Method for producing building material by using desulfurization and denitrification byproducts
Technical Field
The invention relates to a method for producing building materials by using desulfurization and denitrification byproducts.
Background
With the wide popularization of the desulfurization and denitrification process, the problems of treatment and recycling of the flue gas desulfurization and denitrification byproducts are gradually highlighted. At present, the utilization ratio of SOx/NOx control accessory substance is generally on the low side, and a large amount of SOx/NOx control accessory substances are stacked or are abandoned, not only occupy the land, and the resource is wasted, causes secondary pollution easily moreover. Therefore, it is urgently needed to develop a method for reasonably utilizing the desulfurization and denitrification byproducts so as to reduce secondary pollution, protect the environment and realize the resource utilization of waste.
CN108726940A discloses a preparation method of desulfurized fly ash concrete, which takes coarse aggregate and fine aggregate as main raw materials, and adds a small amount of flue gas desulfurization by-products to prepare the desulfurized fly ash concrete. The desulfurized fly ash concrete comprises the following raw materials in parts by weight: 109 parts of coarse aggregate, 61 parts of fine aggregate, 30-45 parts of cement, 5-20 parts of desulfurized fly ash, 17 parts of water and 1-2 parts of additive. Although the invention adds a small amount of desulfurized ash, can save the cement dosage to a certain extent and reduce the construction cost, the application range and the improvement effect are limited, and the method only relates to the resource recycling of the desulfurized ash.
CN102557548B discloses a preparation method of a dry desulfurization byproduct autoclaved brick, which takes 50-75 parts by weight of a dry flue gas desulfurization byproduct, 3-15 parts by weight of a cementing material, 5-29 parts by weight of aggregate and 1-3 parts by weight of an alkaline additive as raw materials, the raw materials and water are stirred in a high-speed strong shear mixer, and then the stirred materials are subjected to compression molding and autoclaved curing treatment in sequence to obtain the autoclaved brick. The density of the autoclaved brick reaches 1650kg/m3A thermal conductivity of less than 0.25w (m)2·k)-1The method has good performance, but the method only carries out resource recycling on the desulfurization byproducts, and the recycling mode is single.
CN109110791B discloses a method for preparing high-purity calcium nitrate by using desulfurization and denitrification byproducts, which comprises the following steps: s1, premixing the desulfurization and denitrification byproducts and water to obtain a premixed solution; stirring the premixed solution, adding an oxidant in the stirring process, stirring, and standing to obtain a mixed solution; carrying out solid-liquid separation on the mixed solution to generate a first filtrate and a first solid component; filtering the first filtrate to produce a first residue and a second filtrate; combining the first residue with a first solid component; mechanically filter-pressing the first solid component, collecting and recycling a filter-pressing cake, and filtering a filter-pressing liquid obtained after filter-pressing to generate a third filter liquid and a second residue; combining the second residue with the first solid component; s2, mixing the second filtrate and the third filtrate of the step S1, evaporating and concentrating, cooling, crystallizing and drying to obtain a crystalline solid containing a water-soluble component of calcium nitrate; s3, mixing and stirring the crystalline solid obtained in the step S2 with an organic solvent, and carrying out solid-liquid separation to generate a second solid component and an organic solvent filtrate; distilling the second solid component under reduced pressure, recycling the generated organic solvent, returning the generated third solid component to the step of S1, and mixing and stirring the third solid component with the desulfurization and denitrification byproducts, the water and the oxidant in the step S1; and distilling the organic solvent filtrate under reduced pressure, continuously recycling the organic solvent, and obtaining a crystallized product which is a high-purity calcium nitrate solid. The method has complex process, needs the steps of multiple filtration, evaporation concentration, reduced pressure distillation and the like, has higher energy consumption and higher production cost, and is not suitable for industrial application.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for producing a building material by using a desulfurization and denitrification byproduct, which can perform desulfurization and denitrification on flue gas efficiently and can recycle the desulfurization and denitrification byproduct as resources.
A method for producing building materials by using desulfurization and denitrification byproducts comprises the following steps:
s1, mixing raw materials including 4-16 parts by weight of iron powder, 1-14 parts by weight of bentonite, 2-20 parts by weight of cement, 20-70 parts by weight of lime powder, 2-14 parts by weight of manganese ore, 4-10 parts by weight of cerium ore, 2-15 parts by weight of cobalt ore and 2-15 parts by weight of pore-forming agent, granulating and drying to obtain a desulfurization and denitrification absorbent;
s2, placing the desulfurization and denitrification absorbent in a flue gas environment for desulfurization and denitrification to obtain a desulfurization and denitrification byproduct;
and S3, producing the building material by using the desulfurization and denitrification byproducts.
According to the method of the present invention, preferably, the pore-forming agent is selected from one or more of coal powder, carbon powder, graphite, urea, ammonium bicarbonate, starch, sawdust, straw, rice hull, natural fiber, citric acid, glucose, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, and polymethyl methacrylate;
the mixing comprises dry mixing and wet mixing, and in the wet mixing process, the volume ratio of the added water to the raw materials is 0.1-0.3: 1;
the drying temperature is 200-300 ℃, and the drying time is 1-5 h.
According to the method of the present invention, preferably, step S3 includes: providing 10-65 parts by weight of desulfurization and denitrification byproducts, 30-85 parts by weight of admixture and 5-25 parts by weight of alkali activator to obtain a building raw material composition;
the admixture is selected from one or more of mineral powder, fly ash, steel slag, silica fume, cement, coal gangue, red mud and water granulated slag;
the alkali activator is one or more selected from caustic alkali, alkali metal-containing salt, and alkaline earth metal-containing hydroxide.
According to the method of the present invention, preferably, step S3 further includes: and mixing the building raw material composition to obtain the cementing material serving as the building material.
According to the method of the present invention, preferably, step S3 further includes: and mixing the building raw material composition and aggregate, and then making bricks and curing to obtain the water permeable bricks serving as building materials.
According to the method of the present invention, preferably, step S3 further includes: and mixing the building raw material composition with plant fibers, and then preparing a fiber cement board serving as a building material through board preparation, maintenance, sanding and edge cutting.
According to the method, the weight ratio of the building raw material composition to the plant fiber is preferably 5-10: 1.
According to the method of the present invention, preferably, step S3 includes: providing 20-50 parts by weight of desulfurization and denitrification byproducts, 10-30 parts by weight of mineral powder, 15-35 parts by weight of fly ash, 1-10 parts by weight of steel slag, 2.5-8 parts by weight of silica fume and 8-20 parts by weight of alkali activator to obtain the building raw material composition.
According to the method of the present invention, preferably, step S3 further includes: and mixing the building raw material composition and aggregate, and then making bricks and curing to obtain the water permeable bricks serving as building materials.
According to the method of the present invention, preferably, step S3 further includes: and mixing the building raw material composition with plant fibers, and then preparing a fiber cement board serving as a building material through board preparation, maintenance, sanding and edge cutting.
The method disclosed by the invention can be used for efficiently desulfurizing and denitrating the flue gas and recycling the desulfurization and denitration byproducts. According to the invention, by optimizing the formula of the desulfurization and denitrification agent, the obtained by-product is matched with other raw materials, and the building materials with good performance, such as cementing materials, water permeable bricks, fiber cement boards and the like, can be manufactured.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited thereto.
First, terms related to the present invention are explained:
the admixture is a powdery mineral substance which is mixed in the concrete during mixing and can improve the performance of the concrete in order to improve the performance of the concrete, save water and adjust the strength grade of the concrete. "admixtures" are divided into active admixtures and inactive admixtures. The active admixture does not harden or has a slow hardening speed, and can be coagulated and hardened to generate strength after being mixed with calcareous materials such as lime, slaked lime and the like by adding water, or react with calcium hydroxide generated by cement hydration to generate hydration products with gelling capacity, such as fly ash, granulated blast furnace slag powder, zeolite powder, silica fume and the like. By inactive admixtures are meant mineral admixtures which are primarily for filling purposes, do not substantially react with the cement component, and do not impair the performance of the cement, such as limestone, ground quartz sand, and the like.
The mineral powder is high-fineness and high-activity powder obtained by water quenching blast furnace slag and carrying out processes such as drying, grinding and the like, is a high-quality concrete admixture and cement admixture, and is also called slag micro powder and granulated blast furnace slag powder.
Fly ash, fine solid particles in the ash of flue gas generated by combustion of fuel, is also called fly ash or soot.
The steel slag is mainly derived from oxides formed by oxidizing elements contained in molten iron and scrap steel, and mainly comprises oxides of calcium, iron, silicon, magnesium, aluminum, manganese, phosphorus and the like.
Silica fume, SiO produced during smelting ferrosilicon and industrial silicon2And Si gas and oxygen in the air are quickly oxidized and condensed to form a superfine silicon powder material, which is also called as micro silicon powder or condensed silica fume.
The coal gangue is solid waste discharged in the coal mining process and the coal washing process, and is a black and gray rock which has lower carbon content and is harder than coal and is associated with a coal bed in the coal forming process.
Red mud, an industrial solid waste discharged when extracting alumina in the aluminum industry, is called red mud because of its large amount of iron oxide and its appearance similar to that of red mud.
The granulated slag is iron-making blast furnace slag, and is formed by rapidly cooling molten blast furnace slag in water.
The alkali activator is a term of art for alkali-activated gelling materials, is called catalyst in chemistry, and generally refers to caustic alkali, silicate, aluminate, phosphate, sulfate, carbonate and other substances containing alkali elements.
Sulfur capacity, weight of sulfur absorbed by the desulfurizing agent per unit weight. The unit is usually mg/g.
Penetration sulfur capacity: under certain use conditions, the desulfurizer can absorb the weight of sulfur when ensuring the index of process purification degree. In the invention, the penetration index of the pollutant outlet of the desulfurizer is 35mg/Nm3。
Nitre volume, which represents the weight of nitrogen oxides absorbed per unit weight of denitrifier. The unit is usually mg/g.
Penetration nitre volume: under certain use conditions, the denitration agent can absorb the weight of nitrogen oxide when ensuring the process purification degree index. In the invention, the penetration index of the pollutant outlet of the denitrifying agent is 50mg/Nm3。
The strength refers to the stress applied when the desulfurization/denitrification absorbent is broken. The unit is usually N/cm.
The invention discovers that the produced desulfurization and denitrification absorbent has higher strength and good desulfurization and denitrification effects by taking iron powder, bentonite, cement, lime powder, manganese ore, cerium ore, cobalt ore and pore-forming agent as raw materials. In addition, the by-product obtained after the desulfurization and denitrification absorbent is used can be combined with other raw materials to produce building materials with good performance. Therefore, the invention provides a method for producing building materials by using desulfurization and denitrification byproducts. As described in detail below.
The method for producing a building material of the present invention comprises three steps: producing desulfurization and denitrification absorbent, producing desulfurization and denitrification byproducts and producing building materials. As described in detail below.
Production of desulfurization and denitrification absorbent
Mixing raw materials containing iron powder, bentonite, cement, lime powder, manganese ore, cerium ore, cobalt ore and a pore-forming agent, granulating, and drying to obtain the desulfurization and denitrification absorbent. In certain embodiments, raw materials consisting of iron powder, bentonite, cement, lime powder, manganese ore, cerium ore, cobalt ore and pore-forming agent are mixed, granulated and dried to obtain the desulfurization and denitrification absorbent.
Mixing the above raw materials to obtain a mixture. Mixing includes dry mixing and wet mixing. The dry mixing time can be 5-25 min, preferably 10-20 min, and more preferably 15-20 min. The wet mixing time can be 15-45 min, preferably 20-40 min, and more preferably 25-35 min. The mixing process can quickly and uniformly mix all the raw materials. In the wet mixing process, the volume ratio of the water addition amount to the raw materials can be 0.1-0.3: 1, preferably 0.15-0.25: 1, and more preferably 0.18-0.23: 1. The proportion can be used for better granulating, and is beneficial to improving the desulfurization and denitrification performance and strength parameters of the desulfurization and denitrification absorbent.
And granulating the mixture to obtain the particles to be dried. The particles to be dried can be spherical or columnar, and are preferably spherical particles with the diameter of 2-10 mm or columnar particles with the diameter of 2-10 mm and the length of 8-15 mm. The desulfurization and denitrification absorbent with the shape and the size can provide higher sulfur capacity and nitrate capacity in the using process and is convenient to replace and store.
And drying the particles to be dried to obtain the desulfurization and denitrification absorbent. The drying temperature may be 200 to 300 ℃, preferably 200 to 280 ℃, and more preferably 200 to 250 ℃. The drying time can be 1-5 h, preferably 1-3.5 h, and more preferably 2-3 h. When the drying temperature is lower than 200 ℃, the penetrating sulfur capacity is less than or equal to 50mg/g, the penetrating nitrate capacity is less than or equal to 25mg/g, and the strength is less than or equal to 180N/cm; when the drying temperature is higher than 300 ℃, the energy consumption is large, the production cost is high, and the method is not suitable for industrial production. According to some embodiments of the invention, the drying is carried out at 200 to 280 ℃ for 1 to 3.5 hours. According to other embodiments of the invention, the desulfurization and denitrification absorbent is dried for 2-3 hours at 200-250 ℃, so that the desulfurization and denitrification absorbent has good sulfur capacity, nitrate capacity and strength, the energy consumption can be reduced, and the production cost can be reduced.
In the invention, the pore-forming agent can be one or more selected from coal powder, carbon powder, graphite, urea, ammonium bicarbonate, starch, sawdust, straw, rice hull, natural fiber, citric acid, glucose, polyethylene glycol, polyvinyl alcohol, polyethylene oxide and polymethyl methacrylate, preferably one or more selected from coal powder, carbon powder, graphite, urea, ammonium bicarbonate and starch, and more preferably urea and/or ammonium bicarbonate. The urea and/or ammonium bicarbonate is/are used as pore-forming agent, the pore distribution of the produced desulfurization and denitrification absorbent is more uniform, and the improvement of the sulfur capacity and the nitrate capacity of the desulfurization and denitrification absorbent is facilitated.
The amount of the iron powder may be 4 to 16 parts by weight, preferably 6 to 14 parts by weight, and more preferably 8 to 12 parts by weight per 100 parts by weight of the raw materials. The bentonite may be used in an amount of 1 to 14 parts by weight, preferably 2 to 10 parts by weight, and more preferably 3 to 8 parts by weight. The amount of the cement used may be 2 to 20 parts by weight, preferably 4 to 15 parts by weight, and more preferably 4 to 8 parts by weight. The lime powder may be used in an amount of 20 to 70 parts by weight, preferably 30 to 65 parts by weight, and more preferably 40 to 60 parts by weight. The amount of the manganese ore may be 2 to 14 parts by weight, preferably 4 to 12 parts by weight, and more preferably 6 to 11 parts by weight. The amount of the cerium ore may be 4 to 10 parts by weight, preferably 4 to 9 parts by weight, and more preferably 4 to 8 parts by weight. The amount of the cobalt ore may be 2 to 15 parts by weight, preferably 3 to 12 parts by weight, and more preferably 4 to 10 parts by weight. The pore-forming agent may be used in an amount of 2 to 15 parts by weight, preferably 4 to 13 parts by weight, and more preferably 5 to 10 parts by weight. The components are cooperated, so that the produced desulfurization and denitrification absorbent has high strength and good desulfurization and denitrification effects.
According to some embodiments of the present invention, when the amount of the manganese ore is less than 2 parts by weight, the penetrating nitrate capacity of the desulfurization and denitrification absorbent is 15mg/g or less; when the amount of the manganese ore is more than 14 parts by weight, the penetrating nitrate capacity of the desulfurization and denitrification absorbent is less than or equal to 10mg/g, and the strength of the desulfurization and denitrification absorbent is poor. When the using amount of the cerium ore is less than 4 parts by weight, the penetrating nitrate capacity of the desulfurization and denitrification absorbent is less than or equal to 13 mg/g; when the amount of the cerium ore is more than 10 parts by weight, the sulfur penetration capacity of the desulfurization and denitrification absorbent is less than or equal to 45mg/g, and the nitrate penetration capacity is less than or equal to 25 mg/g. When the using amount of the cobalt ore is less than 2 parts by weight, the penetrating nitrate capacity of the desulfurization and denitrification absorbent is less than or equal to 20 mg/g; when the using amount of the cobalt ore is more than 15 parts by weight, the penetrating sulfur capacity of the desulfurization and denitrification absorbent is less than or equal to 48mg/g, and the penetrating nitrate capacity is less than or equal to 18 mg/g.
According to some embodiments of the invention, the desulfurization and denitrification absorbent is prepared by mixing, granulating and drying 4-16 parts by weight of iron powder, 1-14 parts by weight of bentonite, 2-20 parts by weight of cement, 20-70 parts by weight of lime powder, 2-14 parts by weight of manganese ore, 4-10 parts by weight of cerium ore, 2-15 parts by weight of cobalt ore and 2-15 parts by weight of pore-forming agent, wherein the drying temperature is 200-300 ℃ and the drying time is 1-5 hours.
According to other embodiments of the invention, 6-14 parts by weight of iron powder, 2-10 parts by weight of bentonite, 4-15 parts by weight of cement, 30-65 parts by weight of lime powder, 4-12 parts by weight of manganese ore, 4-10 parts by weight of cerium ore, 3-12 parts by weight of cobalt ore and 4-13 parts by weight of pore-forming agent are taken as raw materials, and the raw materials are mixed, granulated and dried to obtain the desulfurization and denitrification absorbent; wherein the pore-forming agent is one or more of coal powder, carbon powder, graphite, urea, ammonium bicarbonate and starch; the drying temperature is 200-280 ℃, and the drying time is 1-3.5 h.
According to still other embodiments of the invention, 8-12 parts by weight of iron powder, 3-8 parts by weight of bentonite, 4-8 parts by weight of cement, 40-60 parts by weight of lime powder, 6-11 parts by weight of manganese ore, 4-8 parts by weight of cerium ore, 4-10 parts by weight of cobalt ore and 5-10 parts by weight of pore-forming agent are taken as raw materials, and the raw materials are mixed, granulated and dried to obtain the desulfurization and denitrification absorbent; wherein the pore-forming agent is urea and/or ammonium bicarbonate; the drying temperature is 200-250 ℃, and the drying time is 2-3 h.
Production of desulfurization and denitrification by-products
And (3) placing the desulfurization and denitrification absorbent in a flue gas environment for desulfurization and denitrification to obtain a desulfurization and denitrification byproduct.
In the present invention, the flue gas may be a flue gas containing nitrogen oxides and/or sulfur oxides, and preferably a flue gas containing nitrogen oxides and sulfur oxides. In the invention, the desulfurization and denitrification by-products are preferably crushed to 80-400 meshes.
According to some embodiments of the invention, the desulfurization and denitrification absorbent is loaded on a fixed bed, and then placed in flue gas containing nitrogen oxides and sulfur oxides for flue gas adsorption to obtain a used desulfurization and denitrification absorbent, and then the used desulfurization and denitrification absorbent is ground to a particle size of 100-300 meshes to obtain a desulfurization and denitrification byproduct.
Production of building materials
And providing the desulfurization and denitrification by-product, the admixture and the alkali activator to obtain the building raw material composition. In the invention, the admixture can be one or more selected from mineral powder, fly ash, steel slag, silica fume, cement, coal gangue, red mud and water granulated slag; preferably one or more of mineral powder, fly ash, steel slag and silica fume; more preferably mineral powder, fly ash, steel slag and silica fume. The selection of the substances is beneficial to improving the strength of the building raw material composition in the application process, and simultaneously, other properties are not influenced, so that the application range of the building raw material composition is expanded. According to some embodiments of the present invention, the admixture is a mixture of 10 to 30 parts by weight of mineral powder, 15 to 35 parts by weight of fly ash, 1 to 10 parts by weight of steel slag and 2.5 to 8 parts by weight of silica fume, and the admixture thus formed has good applicability, and the mineral powder, fly ash, steel slag and silica fume in the admixture cooperate with each other, which is not only beneficial to improving the fluidity of the building material before setting and hardening, but also beneficial to increasing the compressive strength and durability of the product.
In the present invention, the alkali activator may be one or more selected from the group consisting of caustic alkali, alkali metal-containing salts, and alkaline earth metal-containing hydroxides; preferably one or more of hydroxides containing alkali metals and hydroxides containing alkaline earth metals; more preferably sodium hydroxide and/or calcium hydroxide. The sodium hydroxide and/or calcium hydroxide are/is used as an alkali activator, so that better synergistic effect can be achieved with the desulfurization and denitrification byproducts, and the activity excitation effect is enhanced.
The amount of the desulfurization and denitrification by-product may be 10 to 65 parts by weight, preferably 20 to 50 parts by weight, and more preferably 30 to 45 parts by weight, per 100 parts by weight of the building raw material composition. When the amount of the desulfurization and denitrification by-product is less than 10 parts by weight, the compressive strength of the building material produced by using the building raw material composition as a raw material is low; when the amount of the desulfurization and denitrification by-product is more than 65 parts by weight, the flexural strength of the building material produced by using the building material composition as a raw material is low.
The amount of the admixture may be 30 to 85 parts by weight, preferably 40 to 70 parts by weight, and more preferably 40 to 55 parts by weight, per 100 parts by weight of the building material composition. When the using amount of the admixture is less than 30 parts by weight, the compactness and compressive strength of the building material produced by taking the building raw material composition as a raw material are lower; when the amount of the admixture is more than 85 parts by weight, the building material produced using the building material composition as a raw material has a low early flexural strength and is liable to have bubble residues.
The alkali activator may be used in an amount of 5 to 25 parts by weight, preferably 8 to 20 parts by weight, and more preferably 10 to 15 parts by weight, per 100 parts by weight of the building material composition. When the amount of the alkali activator is less than 5 parts by weight, the activity-activating effect cannot be achieved; when the amount of the alkali activator is more than 25 parts by weight, the building material produced by using the building raw material composition as a raw material has better early compressive strength and flexural strength, but the subsequent efflorescence problem easily occurs, so that the later compressive strength and flexural strength are poorer.
According to some embodiments of the invention, the construction feedstock composition is made from a feedstock comprising: 10-65 parts by weight of a desulfurization and denitrification byproduct, 30-85 parts by weight of an admixture and 5-25 parts by weight of an alkali activator; wherein the admixture is selected from one or more of mineral powder, fly ash, steel slag, silica fume, cement, coal gangue, red mud and water granulated slag.
According to other embodiments of the present invention, a construction feedstock composition is made from a feedstock comprising: 20-50 parts by weight of desulfurization and denitrification byproducts, 40-70 parts by weight of admixture and 8-20 parts by weight of alkali activator; wherein the admixture is selected from one or more of mineral powder, fly ash, steel slag and silica fume.
According to still further embodiments of the present invention, a construction feedstock composition is made from a feedstock comprising: 30-45 parts of desulfurization and denitrification byproducts, 40-55 parts of admixture and 10-15 parts of alkali activator; wherein the admixture is mineral powder, fly ash, steel slag and silica fume.
In some embodiments, the construction feedstock composition is made from a feedstock comprising: 10-65 parts by weight of desulfurization and denitrification byproducts, 0-40 parts by weight of mineral powder, 10-40 parts by weight of fly ash, 0-20 parts by weight of steel slag, 2-10 parts by weight of silica fume and 5-25 parts by weight of alkali activator.
In other embodiments, the construction feedstock composition is made from a feedstock comprising: 20-50 parts of desulfurization and denitrification byproducts, 10-30 parts of mineral powder, 15-35 parts of fly ash, 1-10 parts of steel slag, 2.5-8 parts of silica fume and 8-20 parts of alkali activator.
In still other embodiments, the construction feedstock composition is made from a feedstock of: 30-45 parts of desulfurization and denitrification byproducts, 15-25 parts of mineral powder, 20-30 parts of fly ash, 2-4 parts of steel slag, 2.5-5 parts of silica fume and 10-15 parts of alkali activator.
The building material is produced by using the building raw material composition. In the present invention, the building material may be a material that can be used in construction works, for example, cement, concrete, a plate material, a brick material, and the like. The concrete will be described in detail below by taking cement, water permeable bricks and fiber cement boards as examples.
Cementitious material
And mixing the building raw material composition to obtain the cementing material. The specific process is as follows:
firstly, dry-mixing the desulfurization and denitrification by-products of the building raw material composition, the admixture and the alkaline activator to obtain the cementing material. The dry blending process may be carried out in a conventional blender or mixer so long as uniform mixing is achieved. According to one embodiment of the invention, the building material composition is dry blended in a ribbon blender.
Preferably, the gelled material is hermetically packaged to avoid the product becoming wet and contaminated.
Water permeable brick
And mixing the building raw material composition and the aggregate, and then making bricks and curing to obtain the water permeable bricks.
The specific process is as follows:
dry-mixing the building raw material composition, the coarse aggregate and the fine aggregate, and adding water for mixing to obtain a semi-dry backing material; and (3) dry-mixing the building raw material composition and the fine aggregate, and adding water for mixing to obtain the semi-dry fabric. When the base material is produced, the weight ratio of the building raw material composition to the fine aggregate to the coarse aggregate can be 85-96: 2-8, preferably 86-94: 3-7, and more preferably 88-90: 5-7. When the fabric is produced, the weight ratio of the building raw material composition to the fine aggregate can be 7-9.5: 1, preferably 8-9.5: 1, and more preferably 8-9: 1. The water permeable brick produced by selecting the above proportion not only has good water permeability, but also has higher breaking strength and splitting tensile strength. The mixing process can be carried out in conventional stirring or mixing apparatus, preferably in a screw mixer.
Distributing, pressing and demoulding to obtain green bricks. The material distribution process can be carried out by adopting a material distribution vehicle. And sequentially laying the bottom material and the face material during laying. After the material distribution is finished, the raw materials can be pressed and formed through extrusion vibration. In the demolding, it is preferable to perform demolding by raising the mold frame while the ram is stationary.
And curing the green bricks to obtain the water permeable bricks. The curing process comprises pre-curing and natural curing. The pre-curing is preferably carried out in a pre-curing kiln, and the pre-curing time can be 6-30 hours, preferably 6-28 hours, and more preferably 8-24 hours. The natural curing is preferably carried out in a curing cellar, and the time for the natural curing can be 6-30 days, preferably 6-28 days, and more preferably 8-28 days.
Fiber cement board
Mixing the building raw material composition with the plant fiber, and then carrying out plate making, maintenance, sanding and edge cutting to obtain the fiber cement plate. The specific process is as follows:
mixing the building raw material composition and the plant fiber, adding water and stirring to obtain slurry. The weight ratio of the plant fiber to the building raw material composition is 1: 5-10; preferably 1: 6-10; more preferably 1:8 to 10. The proportion not only can ensure that the fiber cement board has good impact strength and soaking drying performance, but also can ensure that the fiber cement board keeps lower water absorption and wet expansion rate. When the dosage of the plant fiber is excessive, the fiber cement board has high water absorption rate and poor impact strength, and is easy to agglomerate in the production process, thereby influencing the production; when the amount of the plant fiber is too small, the flexural strength of the fiber cement board is poor. The stirring process can be carried out in conventional stirring equipment, for example a stirrer.
And (3) making a board by adopting a copying method, cutting, and molding (namely putting into a mold) to obtain the molded fiber cement board.
And (3) placing the formed fiber cement board in a curing kiln for curing, demolding, and naturally curing to obtain the cured fiber cement board. The curing time can be 6-24 h, preferably 6-18 h, and more preferably 8-12 h.
And drying the maintained fiber cement board, sanding and trimming to obtain the fiber cement board.
The test method is described below:
1. breakthrough sulfur capacity and breakthrough nitrate capacity: the desulfurization and denitrification absorbent is placed in the test conditions shown in table 1, and the concentration of each pollutant in the simulated flue gas is tested by using a flue gas analyzer, wherein the test endpoint of the penetration sulfur capacity is as follows: SO (SO)2Has an outlet concentration of 35mg/Nm3(ii) a The test endpoint for breakthrough nitre was: NOxHas an outlet concentration of 50mg/Nm3。
TABLE 1
Test conditions Parameter(s)
Initial SO2 2800mg/Nm3
Initial NOx 1000mg/Nm3
Temperature of 140℃
Simulating water content of flue gas 10％
Simulating oxygen content of flue gas 14％
Contact time of materials 7s
2. And (3) testing the strength: GB/T30202.3-2013 'test method of coal granular activated carbon for desulfurization and denitrification' is adopted for testing, and the specific test method is as follows:
1) sample preparation: randomly extracting 20 samples with smooth surfaces, regularity and length-diameter ratio not less than 1;
2) preparing an instrument: adjusting the zero point of the compressive strength instrument;
3) and (3) sample testing: placing each sample in a V-shaped groove of a lower clamp along the axial direction of a cylinder, starting a compressive strength tester, and recording the pressure value at the moment of crushing the sample, wherein the pressure value is measured by 50daN when the pressure value is greater than 50daN (mechanical unit, 1daN is 10N);
4) and (3) calculating the intensity: the average value of 20 measurements is the required intensity.
3. Performance testing of the cement: the performance of the cementitious material was tested according to GB175-2007 Portland Cement for general use.
4. And (3) testing the performance of the water permeable brick: and (4) carrying out performance test on the water permeable brick according to GB/T25993-2010 water permeable pavement brick and water permeable pavement slab.
5. Performance testing of fiber cement boards: the performance of the fiber cement board is measured according to the test method of the fiber cement product in JC/T564.1-2018 fiber reinforced calcium silicate board.
Preparation examples 1 to 9 and comparative preparation examples 1 to 4
S1, weighing raw materials according to the raw material proportion shown in Table 2, conveying the raw materials to a kneading machine, and carrying out dry mixing for 10min to obtain a first mixture; deionized water was added to the first mixture three times (the volume ratio of the amount of water added to the raw materials was 0.12:1), and wet-mixed for 30min to obtain a second mixture.
And S2, conveying the second mixture to a granulator for granulation to obtain cylindrical particles to be dried (the diameter is 5-10 mm, and the length is 8-15 mm).
And S3, placing the particles to be dried in a drying oven, and drying for 2h (the drying temperature is shown in Table 2) to obtain the desulfurization and denitrification absorbent.
S4, placing the desulfurization and denitrification absorbent in an atmosphere containing sulfur oxides and nitrogen oxides for desulfurization and denitrification to obtain the used desulfurization and denitrification absorbent. The performance of the desulfurization and denitrification absorbent was also measured, and the results are shown in Table 3.
TABLE 2
Figure BDA0003233098310000151
TABLE 3
Group of Penetration sulfur capacity (mg/g) Mirabilitum penetration (mg/g) Strength (N/cm)
Preparation example 1 62 35 260
Preparation example 2 52 25 243
Preparation example 3 50 22 205
Preparation example 4 55 21 256
Preparation example 5 58 28 269
Preparation example 6 63 32 220
Preparation example 7 61 33 230
Preparation example 8 58 30 240
Preparation example 9 52 26 208
Comparative preparation example 1 55 12 232
Comparative preparation example 2 35 10 206
Comparative preparation example 3 50 25 180
Comparative preparation example 4 46 21 150
As can be seen from Table 3, the desulfurization and denitrification absorbent produced by the method of the invention has good desulfurization and denitrification performance and compressive strength, and the method has the advantages of low drying temperature, short drying time and low energy consumption.
Examples 1 to 4 and comparative examples 1 to 3
According to the raw material ratio shown in table 4, desulfurization and denitrification byproducts (the used desulfurization and denitrification absorbent in preparation example 1 is ground to 100-200 meshes), mineral powder, fly ash, steel slag, silica fume and an alkali activator (sodium hydroxide) are respectively weighed, and the raw materials are conveyed to a horizontal ribbon mixer and uniformly mixed to obtain the cementing material.
The gelled materials of examples 1 to 4 and comparative examples 1 to 3 were mixed with water in a certain proportion, poured into a 40mm × 40mm × 160mm form, and subjected to a performance test according to GB175-2007 general portland cement after molding, with the results shown in table 5.
TABLE 4
Figure BDA0003233098310000171
TABLE 5
Figure BDA0003233098310000172
As shown in Table 5, the strength of the cementing materials produced in examples 1-4 can reach the standard of 42.5 grades of ordinary Portland cement. In comparative example 1, because no desulfurization and denitrification byproducts are added, the strength performance of the cementing material is slightly inferior to that of examples 1-4. Comparative example 2 the flexural strength and compressive strength of the cement were low due to the use of too little admixture (only 25 parts by weight). In comparative example 3, the use amount of the alkali activator is too much, so that the early compressive strength and the flexural strength of the cementing material are good, but the subsequent problems such as efflorescence and the like are easy to occur, and the later compressive strength and the later flexural strength are poor. The results show that the addition of a proper amount of desulfurization and denitrification byproducts is beneficial to improving the strength of the cementing material, and when the dosage proportion of the desulfurization and denitrification byproducts, the admixture and the alkali activator meets the range claimed by the invention, the cementing material shows good performance.
Examples 5 to 6
First, the used desulfurization and denitrification absorbents of production examples 1 and 4 (prepared according to the formulation shown in production examples 1 and 4) were ground to 100 to 200 mesh as desulfurization and denitrification byproducts of example 5 and example 6, respectively. Then the water permeable brick is produced according to the following steps:
s1, weighing desulfurization and denitrification byproducts, mineral powder, fly ash, steel slag, silica fume, an alkali activator (sodium hydroxide), coarse aggregate and fine aggregate according to the raw material proportion shown in Table 6, conveying the weighed materials to a bed charge spiral stirrer for dry mixing, uniformly mixing, and spraying appropriate amount of water to produce a semi-dry bed charge;
the desulfurization and denitrification byproducts, the mineral powder, the fly ash, the steel slag, the silica fume, the alkali activator (sodium hydroxide) and the fine aggregate are respectively weighed according to the raw material proportion shown in table 7, conveyed into a fabric spiral stirrer to be dry-mixed, uniformly mixed and sprayed with appropriate amount of water to produce the semi-dry fabric.
S2, distributing materials back and forth by adopting a material distributing vehicle, distributing the base material firstly, distributing the base material after the base material reaches a certain height, extruding and vibrating to press and form the raw materials after the material distribution is finished, then keeping the pressing head still, lifting the die frame, and finishing demoulding to obtain the green bricks.
S3, placing the green bricks into a pre-curing kiln for pre-curing for 8-24 hours, stacking the pre-cured green bricks through a stacking machine, and performing natural curing in the curing kiln for 8-28 days to obtain the water permeable bricks.
The performance of the water permeable brick is measured according to the GB/T25993-2010 water permeable pavement brick and water permeable pavement slab standard, and the test result is shown in Table 8.
TABLE 6
Figure BDA0003233098310000181
TABLE 7
Figure BDA0003233098310000182
TABLE 8
Figure BDA0003233098310000191
As can be seen from Table 8, the water permeable brick produced by using the building raw material composition of the invention has good performance and can meet the requirements of GB/T25993-2010 water permeable pavement brick and water permeable pavement slab. Wherein, the rupture strength grade of the water permeable brick can reach Rf4.0 grade, the splitting tensile strength can reach fts4.5 grade, and the water permeability coefficient can reach A grade.
Examples 7 to 8 and comparative example 4
S1, weighing desulfurization and denitrification byproducts (the used desulfurization and denitrification absorbent in preparation example 1 is ground to 100-200 meshes), mineral powder, fly ash, steel slag, silica fume, an alkali activator (sodium hydroxide) and plant fibers (pulp fibers) according to the raw material proportion shown in Table 9, placing the materials in a stirrer, and adding water to stir to obtain slurry.
S2, adopting a preparation process of a copying method, putting the slurry into a net box, copying by a net wheel, contacting the net wheel with the felt, and adhering the slurry on the felt to form a material layer with a certain thickness. The bed of material dewaters step by step through the vacuum box along with the coarse cotton cloth, contacts with a shaping section of thick bamboo afterwards, glues the bed of material on the coarse cotton cloth to a shaping section of thick bamboo, along with a shaping section of thick bamboo constantly contacts with the coarse cotton cloth, the bed of material is thicker and thicker, when reaching required thickness, through the cutting of cutting machine, go up the mould, obtain fashioned fiber cement board.
And S3, placing the formed fiber cement board in a curing kiln for curing for 8 hours, then demolding, and naturally curing to obtain the cured fiber cement board.
S4, placing the maintained fiber cement board in a drying kiln for drying, and further removing water; sanding by using a sander to ensure that the surface of the plate is smooth and the thickness of the plate is consistent; and finally, cutting the sanded fiber cement board by using an edge trimmer to obtain the fiber cement board.
The performance of the fiber cement board was measured according to the test method of fiber cement products in JC/T564.1-2018 fiber reinforced calcium silicate board, and the test results are shown in Table 10.
TABLE 9
Figure BDA0003233098310000201
Watch 10
Figure BDA0003233098310000202
As can be seen from Table 10, the properties of the fiber cement boards produced from the building material composition of the present invention can meet the requirements of the asbestos-free calcium silicate boards A in JC/T564.1-2018 fiber reinforced calcium silicate boards. It can be known from the product performances of examples 7 to 8 and comparative example 4 that the addition amount of the plant fiber can affect the water absorption rate and the impact strength of the board, and when the plant fiber is used in an excessive amount, the fiber cement board has high water absorption rate and poor impact strength, and is easy to agglomerate in the production process to affect the production.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.

Claims (10)

1. A method for producing building materials by using desulfurization and denitrification byproducts is characterized by comprising the following steps:
s1, mixing raw materials including 4-16 parts by weight of iron powder, 1-14 parts by weight of bentonite, 2-20 parts by weight of cement, 20-70 parts by weight of lime powder, 2-14 parts by weight of manganese ore, 4-10 parts by weight of cerium ore, 2-15 parts by weight of cobalt ore and 2-15 parts by weight of pore-forming agent, granulating and drying to obtain a desulfurization and denitrification absorbent;
s2, placing the desulfurization and denitrification absorbent in a flue gas environment for desulfurization and denitrification to obtain a desulfurization and denitrification byproduct;
and S3, producing the building material by using the desulfurization and denitrification byproducts.
2. The method according to claim 1, wherein the pore-forming agent is selected from one or more of pulverized coal, carbon powder, graphite, urea, ammonium bicarbonate, starch, sawdust, straw, rice hull, natural fiber, citric acid, glucose, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, and polymethyl methacrylate;
the mixing comprises dry mixing and wet mixing, and in the wet mixing process, the volume ratio of the added water to the raw materials is 0.1-0.3: 1;
the drying temperature is 200-300 ℃, and the drying time is 1-5 h.
3. The method according to claim 1 or 2, wherein step S3 comprises: providing 10-65 parts by weight of desulfurization and denitrification byproducts, 30-85 parts by weight of admixture and 5-25 parts by weight of alkali activator to obtain a building raw material composition;
the admixture is selected from one or more of mineral powder, fly ash, steel slag, silica fume, cement, coal gangue, red mud and water granulated slag;
the alkali activator is one or more selected from caustic alkali, alkali metal-containing salt, and alkaline earth metal-containing hydroxide.
4. The method according to claim 3, wherein step S3 further comprises: and mixing the building raw material composition to obtain the cementing material serving as the building material.
5. The method according to claim 3, wherein step S3 further comprises: and mixing the building raw material composition and aggregate, and then making bricks and curing to obtain the water permeable bricks serving as building materials.
6. The method according to claim 3, wherein step S3 further comprises: and mixing the building raw material composition with plant fibers, and then preparing a fiber cement board serving as a building material through board preparation, maintenance, sanding and edge cutting.
7. The method according to claim 6, wherein the weight ratio of the construction raw material composition to the plant fiber is 5-10: 1.
8. The method according to claim 1 or 2, wherein step S3 comprises: providing 20-50 parts by weight of desulfurization and denitrification byproducts, 10-30 parts by weight of mineral powder, 15-35 parts by weight of fly ash, 1-10 parts by weight of steel slag, 2.5-8 parts by weight of silica fume and 8-20 parts by weight of alkali activator to obtain the building raw material composition.
9. The method according to claim 8, wherein step S3 further comprises: and mixing the building raw material composition and aggregate, and then making bricks and curing to obtain the water permeable bricks serving as building materials.
10. The method according to claim 8, wherein step S3 further comprises: and mixing the building raw material composition with plant fibers, and then preparing a fiber cement board serving as a building material through board preparation, maintenance, sanding and edge cutting.
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