CN114671633B - Full-solid-waste clinker-free cementing material, conductive mortar and preparation method thereof - Google Patents

Full-solid-waste clinker-free cementing material, conductive mortar and preparation method thereof Download PDF

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CN114671633B
CN114671633B CN202210481974.0A CN202210481974A CN114671633B CN 114671633 B CN114671633 B CN 114671633B CN 202210481974 A CN202210481974 A CN 202210481974A CN 114671633 B CN114671633 B CN 114671633B
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slag
powder
ash
waste
red mud
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CN114671633A (en
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刘益良
苏幼坡
徐国强
李云霞
李宗杰
杨桂华
白力改
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North China University of Science and Technology
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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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/28—Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
    • 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
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/90—Electrical properties
    • C04B2111/94—Electrically conducting materials
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • 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)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention belongs to the technical field of solid waste application in building materials, and particularly relates to a full-solid waste clinker-free cementing material, conductive mortar and a preparation method thereof.

Description

All-solid-waste clinker-free cementing material, conductive mortar and preparation method thereof
Technical Field
The invention belongs to the technical field of solid waste application in building materials, and particularly relates to a full-solid waste clinker-free cementing material, conductive mortar and a preparation method thereof.
Background
The large amount of landfill or stockpiling of industrial solid wastes causes serious pollution to air, land and water. At present, the accumulated industrial solid waste in China is about 620 hundred million tons, and the annual newly added stock exceeds 35 hundred million tons. The bulk industrial solid waste in China is mainly tailings, fly ash, coal gangue, smelting waste slag, coal-fired furnace slag and desulfurized gypsum, and accounts for 78% of the total amount of the industrial solid waste. In recent years, the amount of biomass incineration ash, such as rice hull ash, discharged has increased year by year. The industrial solid wastes are dumped and discarded or stored in different non-environment-friendly modes, so that the land is occupied, the environment is polluted, and the human health, the growth and the survival of animals and plants are seriously harmed. CO emitted by cement industry 2 About 5 to 7 percent of the total global emission, and the comprehensive utilization of multi-path solid waste resources becomes a necessary trend under the guidance of a double-carbon target.
Electrically conductive concrete has important applications in military, construction industry and road deicing. In combination with the power supply and specially configured electrodes, the conductive concrete can be used for deicing roads, sidewalks, bridges and runways. When cast as an overlay, the conductive concrete with very low resistivity can act as a secondary anode in existing cathodic protection systems. In addition, conductive concrete can attenuate electromagnetic and radio waves, can be used to protect computer equipment from eavesdropping, and protect electrical and electronic equipment from interference.
For example, chinese patent CN104310941A discloses an alkali slag-based grouting filler material, which is prepared by using alkali slag and fly ash as main raw materials and adding a proper amount of an active agent, and solves the problem of accumulation of industrial alkali slag and prepares an alkali slag building material. For another example, the chinese patent CN110981232B discloses a steel slag doped adhesive and a preparation method thereof, which uses steel slag, fly ash, gypsum, cement clinker, sodium carbonate, etc. as main raw materials, and solves the problems of low strength, poor stability, low activity, etc. of a large doped steel slag cementing material. For another example, chinese patent CN112723764A discloses a red mud-based cementitious material, a red mud-based lightweight aggregate concrete and a preparation method thereof, wherein red mud or red mud-based waste residues, aluminum residues, desulfurized gypsum and limestone tailings are dried, ground and calcined to obtain red mud-based cementitious material clinker, and then mixed and ground with desulfurized gypsum to prepare the red mud-based cementitious material, so that the durability is improved and the water absorption rate is reduced.
The above patent technologies all adopt the fly ash which is recycled for building materials such as concrete, so the utilization amount of high-quality fly ash is small. The invention is applied to the low utilization rate of high carbon fly ash or biomass ash, and the resource utilization is urgently needed. The Chinese patent CN104310941A and the Chinese patent CN112723764A both adopt activating agents as commodity chemical reagents, the Chinese patent CN110981232B adopts a high-temperature calcination activation method, the production cost is increased, and the exciting agent adopted by the method is a solid waste material, so the cost is extremely low. The carbon fiber and graphite are doped into the Chinese invention patent CN112723764A, so that the concrete obtains the conductive property, and the material cost is greatly improved.
Disclosure of Invention
Aiming at the defects of the problems, the invention provides a full-solid waste clinker-free cementing material, conductive mortar and a preparation method thereof, all the raw materials used by the invention are solid waste materials, only the raw materials are dried, ground and screened, and chemical reagents and high-temperature calcination are not needed, so that the utilization way of solid waste is improved, and the cost is extremely low; the conductive material is added into the material, so that the product has special application, high added value, environmental protection and sustainability.
In order to realize the technical scheme, the invention is realized by the following technical scheme:
an all-solid-waste clinker-free cementitious material comprising: the cementing material is formed by mixing various solid waste powders, wherein the mixed powder is alkali slag, steel slag, red mud, waste gypsum, biomass ash and slag; the proportion of each component is 5 to 15 percent of alkaline residue, 5 to 15 percent of steel slag, 5 to 15 percent of red mud, 5 to 25 percent of waste gypsum, 10 to 30 percent of biomass ash and 15 to 65 percent of slag.
The technical scheme of the invention is further improved as follows: the waste gypsum is any one of desulfurized gypsum, phosphogypsum and fluorgypsum; the biomass ash is any one of rice hull ash, plant ash, straw ash, wood ash and bagasse ash.
A preparation method of a full-solid waste clinker-free cementing material comprises the following steps:
step 1, according to the weight parts of 5-15% of alkaline residue, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 10-30% of biomass ash and 15-65% of slag, respectively dehydrating, drying, grinding and screening by a mesh for later use;
and 2, fully mixing the alkali slag powder, the steel slag powder, the red mud powder, the waste gypsum powder, the biomass ash powder and the slag powder in a mixer for 3 minutes to uniformly mix the powders, wherein the mixed powder is the full-solid waste clinker-free cementing material.
The technical scheme of the invention is further improved as follows: in the step 1, after the alkaline residue, the steel slag and the slag are respectively dried at the temperature of 100 +/-5 ℃ for 2 hours, the mixture is naturally cooled to the normal temperature, and then respectively ground and sieved by a 325-mesh sieve to respectively obtain alkaline residue powder, steel slag powder and slag powder; drying red mud at the temperature of 100 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, and sieving through a 325-mesh sieve to obtain red mud powder; drying the waste gypsum at the temperature of 50 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, and sieving through a 325-mesh sieve to obtain waste gypsum powder; and drying the biomass ash at the temperature of 25 +/-5 ℃ for 0.5-1 hour, and naturally cooling to the normal temperature for later use.
The conductive mortar mainly comprises a full-solid waste clinker-free cementing material, copper slag and water; the all-solid-waste clinker-free cementing materials are respectively alkali slag powder, steel slag powder, red mud, waste gypsum powder, biomass ash and slag powder, and the powder proportion is 5-15% of alkali slag, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 10-30% of biomass ash and 15-65% of slag; wherein the waste gypsum is any one of desulfurized gypsum, phosphogypsum and fluorgypsum; the biomass ash is any one of rice hull ash, plant ash, straw ash, wood ash and bagasse ash; the copper slag amount is 200-300% of the total mass of the all-solid waste clinker-free cementing material, and the water amount is 40-50% of the total mass of the all-solid waste clinker-free cementing material.
The technical scheme of the invention is further improved as follows: the components of the full-solid waste clinker-free cementing material can be replaced by alkaline residue powder, steel slag powder, red mud, waste gypsum powder, high carbon fly ash and slag powder, and the powder proportion is 5-15% of alkaline residue, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 15-65% of slag and 10-30% of high carbon fly ash.
A preparation method of conductive mortar comprises the following steps:
step 1, respectively drying and dehydrating 5-15% of alkaline residue, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 15-65% of slag and 10-30% of high carbon fly ash in parts by weight, grinding and screening by a mesh sieve for later use;
step 2, fully mixing the alkali slag powder, the steel slag powder, the red mud, the waste gypsum powder, the slag powder and the high-carbon fly ash in a mixer for 3 minutes to uniformly mix the powders, wherein the mixed powder is a full-solid waste clinker-free cementing material;
and 3, adding copper slag powder into the clean slurry of the all-solid-waste clinker-free cementing material, adding water accounting for 50% of the total mass of the all-solid-waste clinker-free cementing material, and continuously stirring for 3 minutes to obtain the conductive mortar of the all-solid-waste clinker-free cementing material, namely the conductive mortar.
The technical scheme of the invention is further improved as follows: in the step 1, after the alkaline residue, the steel slag and the slag are respectively dried at the temperature of 100 +/-5 ℃ for 2 hours, the mixture is naturally cooled to the normal temperature, and then respectively ground and sieved by a 325-mesh sieve to respectively obtain alkaline residue powder, steel slag powder and slag powder; drying the red mud at the temperature of 100 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, and sieving through a 325-mesh sieve to obtain the red mud; drying the waste gypsum at the temperature of 50 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, and sieving through a 325-mesh sieve to obtain waste gypsum powder; sieving the high carbon fly ash with a 325-mesh sieve for later use.
The technical scheme of the invention is further improved as follows: in the step 3, after the copper slag is dried for 2 hours at the temperature of 100 +/-5 ℃, the copper slag is naturally cooled to the normal temperature, ground and sieved by a 200-mesh sieve, and copper slag powder is obtained.
The technical scheme of the invention is further improved as follows: in the step 1, according to the weight parts of 5-15% of alkaline residue, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 10-30% of biomass ash and 15-65% of slag, the materials are respectively dried, dehydrated, ground and sieved for later use.
Compared with the prior art, the full-solid-waste clinker-free cementing material, the conductive mortar and the preparation method thereof have the following beneficial effects:
1. the invention provides a full-solid waste clinker-free cementing material, which is characterized in that the net slurry of the full-solid waste clinker-free cementing material is increased along with the maintenance time to generate hydrated calcium silicate gel and ettringite products, so as to generate strength, and the full-solid waste clinker-free cementing material can be mixed with fine aggregate to form full-solid waste clinker-free cementing material mortar, and mixed with fine aggregate and coarse aggregate to form full-solid waste clinker-free cementing material concrete.
2. In the all-solid-waste clinker-free cementing material, caustic sludge, steel slag and red mud are used as alkaline excitants, waste gypsum is used as a sulfate excitant, and slag and biomass ash are used as active materials; the slag and the biomass ash generate hydrated calcium silicate gel and ettringite under the double excitation action of alkali-sulfate, so that the slurry has cohesiveness and can replace cement; meanwhile, all the raw materials used in the invention are solid waste materials, and only the raw materials need to be dried, ground and screened, and chemical reagents and high-temperature calcination are not needed, so that the invention is an environment-friendly sustainable cementing material.
3. According to the conductive mortar provided by the invention, the cementing materials of alkaline residue, steel slag and red mud in the conductive mortar are used as alkaline excitants, waste gypsum is used as a sulfate excitant, and slag and high-carbon fly ash are used as active materials; the slag and the high carbon fly ash generate hydrated calcium silicate gel and ettringite under the double excitation action of alkali-sulfate, so that the slurry has cohesiveness and can be used for replacing cement, and meanwhile, the high carbon fly ash and the copper slag in the conductive mortar are used as conductive media, so that the hardened mortar has conductivity.
4. According to the conductive mortar provided by the invention, all raw materials are solid waste materials, only the raw materials are required to be dried, ground and screened, chemical reagents and high-temperature calcination are not required, the utilization path of solid waste is improved, the conductivity of the product enables the product to have special purposes, and the conductive mortar is a sustainable material with high added value and environmental friendliness.
Detailed Description
The technical solution of the present invention will be clearly and completely described by the following detailed description. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The cementing material consists of mixed powder consisting of various solid waste powders, wherein the mixed powder consists of 5 to 15 percent of alkali slag, 5 to 15 percent of steel slag, 5 to 15 percent of red mud, 5 to 25 percent of waste gypsum, 15 to 65 percent of slag and 10 to 30 percent of biomass ash. Wherein the waste gypsum can be desulfurized gypsum, phosphogypsum and fluorgypsum, and the biomass ash can be rice hull ash, wood ash or bagasse ash.
A preparation method of a full-solid waste clinker-free cementing material comprises the following steps:
s1, respectively preparing alkaline residue, steel slag, waste gypsum, biomass ash and slag into alkaline residue powder, steel slag powder, waste gypsum powder and slag powder; the red mud needs to be dried and dehydrated, and the dried red mud can be directly used after being screened; the biomass ash can be directly used after being dried; the waste gypsum can be desulfurized gypsum, phosphogypsum and fluorgypsum, and the biomass ash can be rice husk ash, wood ash or bagasse ash;
the method comprises the following specific steps of:
(d1) Drying the caustic sludge at 100 +/-5 ℃ for 2 hours, standing and cooling to normal temperature;
(d2) Grinding the dried alkaline residue and sieving the ground alkaline residue through a 325-mesh sieve to obtain alkaline residue powder;
the method comprises the following specific steps of:
(d1) Drying the steel slag at the temperature of 100 +/-5 ℃ for 2 hours, standing and cooling to normal temperature;
(d2) Grinding the dried steel slag and sieving the ground steel slag through a 325-mesh sieve to obtain steel slag powder;
the method comprises the following specific steps of:
(d1) Drying waste gypsum at 50 +/-5 ℃ for 2 hours, standing and cooling to normal temperature;
(d2) Grinding the dried waste gypsum and sieving the ground waste gypsum through a 325-mesh sieve to obtain waste gypsum powder;
the concrete steps for preparing the slag powder are as follows:
(d1) Drying the slag at 100 +/-5 ℃ for 2 hours, standing and cooling to normal temperature;
(d2) Grinding the dried slag and sieving the ground slag through a 325-mesh sieve to obtain slag powder;
the specific steps of drying the red mud are as follows:
(d1) Drying the red mud at the temperature of 100 +/-5 ℃, standing for 2 hours, and cooling to normal temperature;
(d2) The dried red mud does not need to be ground and is sieved by a 325-mesh sieve to obtain red mud powder;
the biomass ash comprises the following specific steps:
(d1) Drying the biomass ash at the temperature of 25 +/-5 ℃ for 0.5-1 hour, and naturally cooling to normal temperature;
(d2) The product can be used;
s2, fully mixing 10% of alkaline residue powder, 15% of steel slag powder, 5% of red mud, 10% of waste gypsum powder, 45% of slag powder and 15% of biomass ash prepared in the step S1 in a stirrer for 3 minutes to uniformly mix the powder; the mixed powder is the full solid waste clinker-free cementing material.
According to the all-solid-waste clinker-free cementing material prepared by the embodiment, the all-solid-waste clinker-free cementing material prepared by completely adopting the all-solid-waste material without high-temperature calcination and chemical exciting reagent is prepared by using the alkaline solid waste as an alkaline exciting agent, the sulfate solid waste as a sulfate exciting agent and alkali-sulfate coupling excitation of the solid waste with the pozzolan activity. The caustic sludge is waste material in alkali making industry, the steel slag is a byproduct in steel making process, the red mud is solid waste generated in alumina production process by bauxite, and the caustic sludge, the steel slag and the red mud are alkaline, so the caustic sludge, the steel slag and the red mud are used as alkaline excitants. The desulfurized gypsum is used for absorbing SO in the process of flue gas emission 2 The phosphogypsum is a solid waste produced in a wet-process phosphoric acid process, the fluorgypsum is a byproduct of preparing hydrogen fluoride from sulfuric acid and fluorspar, and the desulfurized gypsum, the phosphogypsum and the fluorgypsum all contain a large amount of calcium sulfate and can be used as a sulfate excitant. Rice hull ash is ash generated by generating electricity or steam and burning rice hulls outdoors, wood ash is residue generated by burning wood and products (wood chips, sawdust and barks) thereof for generating electricity or other purposes, and bagasse ash is a product obtained by burning residue obtained by extracting juice from sugar cane in a sugar making process. Rice husk ash and wood ashBagasse ash contains a large amount of SiO 2 、Al 2 O 3 And Fe 2 O 3 Has volcanic ash activity. The invention adopts alkaline residue, steel slag and red mud as alkaline excitant, and waste gypsum as sulfate excitant, wherein the waste gypsum can be desulfurized gypsum, phosphogypsum or fluorgypsum, slag and biomass ash are jointly excited, and the biomass ash can be rice hull ash, wood ash or bagasse ash. All the raw materials used in the invention are solid waste materials, only the raw materials are required to be dried, ground and screened, and chemical reagents and high-temperature calcination are not required, so that the invention is an environmentally-friendly and sustainable cementing material.
The mechanical property experiment of the full solid waste clinker-free cementing material is as follows;
the experimental method comprises the following steps: according to the national standard JGJ 70, 0.5 time of water and 3 times of standard sand of powder mass are mixed into a full-solid waste clinker-free cementing material (powder) to prepare mortar, the mixed mortar is put into a bottomed test mold of 70.7mm multiplied by 70.7mm, the test mold is placed in a standard curing box with the temperature of 20 +/-2 ℃ and the relative humidity of more than 90 percent after being vibrated and formed, the test mold is placed in the environment of 20 +/-5 ℃ for 24 +/-2 hours after being detached, and the compressive strength of the test piece can reach 25MPa by using a cement press when the test piece is cured to the age of 28 days.
Figure BDA0003627892050000081
Chart 1
The above graph 1 is: the prepared steel slag excited rice husk ash mortar has the proportioning and mechanical properties.
Figure BDA0003627892050000082
Chart 2
The above graph 2 is: the prepared steel slag excited wood ash mortar has the proportioning and mechanical properties.
The mass in each of the graphs 1 and 2 is based on the sum of the mass of the mixed powder composed of the solid waste powder. The results of the graphs 1 and 2 show that the slag and the biomass ash generate hydrated calcium silicate gel and ettringite under the double excitation action of alkali-sulfate, so that the high-strength and all-solid-waste clinker-free cementing material can replace low-grade cement, and can be used for foundation pit backfill, groove backfill, goaf backfill, temporary building engineering and the like.
Example 2
The conductive mortar consists of a full-solid waste clinker-free cementing material, copper slag and water; the full-solid waste clinker-free cementing material consists of alkaline residue powder, steel slag powder, red mud, waste gypsum powder, high carbon fly ash and slag powder, wherein the powder comprises 5-15% of alkaline residue, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 15-65% of slag and 10-30% of high carbon fly ash in proportion; wherein the waste gypsum can be desulfurized gypsum, phosphogypsum and fluorgypsum; the mixing water consumption in the conductive mortar is 50% of the total mass of the all-solid-waste clinker-free cementing material, and the copper slag consumption is 300% of the total mass of the all-solid-waste clinker-free cementing material.
A preparation method of conductive mortar comprises the following steps:
s1, respectively taking alkaline residue, steel slag, waste gypsum, high carbon fly ash, red mud, slag and copper slag, and respectively preparing alkaline residue powder, steel slag powder, waste gypsum powder, slag powder and copper slag powder; the red mud needs to be dried and dehydrated, and the dried red mud and the high carbon fly ash can be directly used after being screened; the waste gypsum can be desulfurized gypsum, phosphogypsum and fluorgypsum.
The specific steps for preparing the caustic sludge powder are as follows:
(d1) Drying the caustic sludge at the temperature of 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) And grinding the dried alkaline residue and sieving the ground alkaline residue through a 325-mesh sieve to obtain alkaline residue powder.
The method comprises the following specific steps of:
(d1) Drying the steel slag at the temperature of 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried steel slag was ground and sieved through a 325 mesh sieve to obtain steel slag powder.
The method comprises the following specific steps of:
(d1) Drying the waste gypsum at 50 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried waste gypsum was ground and sieved through a 325 mesh sieve to obtain waste gypsum powder.
The specific steps of drying the red mud are as follows:
(d1) Drying the red mud at the temperature of 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried red mud does not need to be ground and is sieved by a 325-mesh sieve to obtain red mud powder.
The concrete steps for preparing the slag powder are as follows:
(d1) Drying slag at 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried slag was ground and sieved through a 325-mesh sieve to obtain slag powder.
The method comprises the following specific steps of:
(d1) Drying the copper slag at the temperature of 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried copper slag was ground and sieved through a 200-mesh sieve to obtain slag powder.
The specific steps for preparing the high carbon fly ash are as follows:
(d1) Sieving the high carbon fly ash through a 200-mesh sieve at normal temperature, and then using the high carbon fly ash.
S2, uniformly mixing 10% of alkaline residue powder, 15% of steel slag powder, 5% of red mud, 10% of waste gypsum powder, 45% of slag powder and 15% of high-carbon fly ash prepared in the step S1; the mixed powder is the full-solid waste clinker-free cementing material;
s3, adding mixing water into the mixed powder in the step S2, wherein the mixing water accounts for 50% of the total mass of the all-solid-waste clinker-free cementing material, and continuously stirring for 3 minutes to obtain pure slurry of the all-solid-waste clinker-free cementing material;
s4, adding copper slag powder into the clean slurry of the full-solid waste clinker-free cementing material in the step S3, wherein the using amount of the copper slag powder is 300% of the total mass of the full-solid waste clinker-free cementing material, adding mixing water with the using amount of 50% of the total mass of the full-solid waste clinker-free cementing material, and continuously stirring for 3 minutes to obtain the conductive mortar of the full-solid waste clinker-free cementing material, namely the conductive mortar. The above S2, S3 and S4 are all operated at normal temperature.
In the conductive mortar prepared according to the embodiment, alkaline solid wastes are used as an alkaline activator, sulfate solid wastes are used as a sulfate activator, and alkali-sulfate coupling is used for exciting solid wastes with volcanic ash activity, so that a full-solid-waste clinker-free cementing material which is prepared from solid wastes completely and does not need high-temperature calcination or chemical activating agents is prepared, copper slag is used as an aggregate, and the conductive mortar of the full-solid-waste material is prepared and used as a groove backfill and a roadbed material for removing pavement icing. The caustic sludge is waste material in alkali making industry, the steel slag is a byproduct in steel making process, the red mud is solid waste generated in alumina production process by bauxite, and the caustic sludge, the steel slag and the red mud are alkaline, so the caustic sludge, the steel slag and the red mud are used as alkaline excitants. The desulfurized gypsum is used for absorbing SO in the process of flue gas emission 2 The later generated waste, phosphogypsum is the solid waste generated in the wet-process phosphoric acid process, fluorgypsum is a byproduct of preparing hydrogen fluoride by using sulfuric acid and fluorspar, and the desulfurized gypsum, the phosphogypsum and the fluorgypsum all contain a large amount of calcium sulfate and can be used as a sulfate excitant. High carbon fly ash refers to fly ash with high content of unburned carbon particles, and the recovery rate is low. Slag is waste obtained by rapidly cooling a melt in an iron-making process. High carbon fly ash and slag containing a large amount of SiO 2 、Al 2 O 3 And Fe 2 O 3 Has volcanic ash activity. Copper slag is a granular industrial waste material generated from ores in the copper smelting process, and although the copper slag can be beneficially reused in the aspects of grinding tools, road construction, ballast and the like, a considerable amount of copper slag is treated in a refuse landfill, and the copper slag can be used as fine aggregate to replace natural sand. The invention adopts alkaline residue, steel slag and red mud as alkaline excitant, and waste gypsum as sulfate excitant, wherein the waste gypsum can be desulfurized gypsum, phosphogypsum or fluorgypsum, the slag and the high carbon fly ash are jointly excited, and the slag and the high carbon fly ash generate hydrated silicon under the double excitation action of alkali and sulfateCalcium carbonate and ettringite become a full-solid waste clinker-free cementing material, and copper slag with conductive performance is doped to prepare the clinker-free conductive mortar which is completely used and is completely used. The raw materials used in the invention are all solid waste materials, only the raw materials are required to be dried, ground and screened, chemical reagents and high-temperature calcination are not required, the utilization approach of the solid waste is improved, the product has special application due to the conductivity, and the product is a sustainable material with high added value and environmental friendliness.
The invention relates to a mechanical property experiment of conductive mortar of a full-solid waste clinker-free cementing material;
the experimental method comprises the following steps: according to the national standard JGJ 70, 0.5 time of water and 3 times of copper slag of powder mass are mixed into a full-solid waste clinker-free cementing material (powder) to prepare mortar, the mixed mortar is put into a bottomed test mould of 70.7mm multiplied by 70.7mm, the test mould is placed in a 20 +/-5 ℃ environment for 24 +/-2 hours after vibration molding, the test mould is removed and then is immediately put into a standard curing box with the temperature of 20 +/-2 ℃ and the relative humidity of more than 90 percent, and after the test piece is cured to 28 days, the compressive strength of the test piece can reach 25MPa by using a cement press.
Figure BDA0003627892050000111
Chart 3
The above chart 3 is: the prepared conductive mortar of the full-solid-waste clinker-free cementing material has the resistance and the mechanical property in proportion.
The masses in the chart 3 are all based on the total mass of the cementing material (the sum of the masses of the caustic sludge, the steel slag, the red mud, the gypsum, the slag and the high carbon fly ash).
In the embodiment, the results of the chart show that the slag and the high-carbon fly ash generate hydrated calcium silicate gel and ettringite under the double excitation action of alkali-sulfate, so that the strength is generated, and the full-solid waste clinker-free cementing material can replace low-grade cement. After the cementing material is mixed with water and copper slag powder, the conductive mortar is obtained and used as a groove backfill and a roadbed material to remove road surface icing, and meanwhile, the high carbon fly ash is combined with the steel slag, so that the conductive mortar has better conductivity.
Example 3
The conductive mortar consists of a full-solid waste clinker-free cementing material, copper slag and water; the full-solid waste clinker-free cementing materials are respectively caustic sludge, steel slag, red mud, waste gypsum, biomass ash and slag, and are respectively dried, ground and sieved to prepare powder, wherein the powder comprises 5-15% of caustic sludge, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 10-30% of biomass ash and 15-65% of slag; wherein the waste gypsum is any one of desulfurized gypsum, phosphogypsum and fluorgypsum, and the biomass ash is any one of rice hull ash, plant ash, straw ash, wood ash and bagasse ash; the mixing water consumption in the conductive mortar is 40% of the total mass of the all-solid-waste clinker-free cementing material, and the copper slag consumption is 200% of the total mass of the all-solid-waste clinker-free cementing material.
A preparation method of conductive mortar comprises the following steps:
s1, respectively taking alkaline residue, steel slag, waste gypsum, red mud, biomass ash, slag and copper slag, and respectively preparing alkaline residue powder, steel slag powder, waste gypsum powder, slag powder and copper slag powder; the red mud needs to be dried and dehydrated, and the dried red mud and biomass ash can be directly used after being slightly dried; the waste gypsum can be desulfurized gypsum, phosphogypsum and fluorgypsum.
The method comprises the following specific steps of:
(d1) Drying the caustic sludge at the temperature of 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) And grinding the dried alkaline residue and sieving the ground alkaline residue through a 325-mesh sieve to obtain alkaline residue powder.
The method comprises the following specific steps of:
(d1) Drying the steel slag at the temperature of 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried steel slag was ground and sieved through a 325 mesh sieve to obtain steel slag powder.
The method comprises the following specific steps of:
(d1) Drying the waste gypsum at 50 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried waste gypsum was ground and sieved through a 325 mesh sieve to obtain waste gypsum powder.
The specific steps of drying the red mud are as follows:
(d1) Drying red mud at 100 + -5 deg.C, standing, and cooling to normal temperature
(d2) The dried red mud is not needed to be ground and is sieved by a 325-mesh sieve, so that the red mud powder is obtained.
The concrete steps for preparing the slag powder are as follows:
(d1) Drying slag at 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried slag was ground and sieved through a 325-mesh sieve to obtain slag powder.
The method comprises the following specific steps of:
(d1) Drying the copper slag at the temperature of 100 +/-5 ℃, standing and cooling to normal temperature;
(d2) The dried copper slag was ground and sieved through a 200-mesh sieve to obtain slag powder.
The biomass ash comprises the following specific steps:
(d1) Drying the biomass ash at the temperature of 25 +/-5 ℃ for 0.5-1 hour, and naturally cooling to normal temperature;
(d2) The product can be used;
s2, uniformly mixing 10% of alkaline residue powder, 15% of steel slag powder, 5% of red mud, 10% of waste gypsum powder, 45% of slag powder and 15% of biomass ash prepared in the step S1; the mixed powder is the full solid waste clinker-free cementing material;
s3, adding mixing water into the mixed powder in the step S2, wherein the mixing water accounts for 50% of the total mass of the all-solid-waste clinker-free cementing material, and continuously stirring for 3 minutes to obtain pure slurry of the all-solid-waste clinker-free cementing material;
and S4, adding copper slag powder into the clean slurry of the all-solid-waste clinker-free cementing material in the step S3, wherein the using amount of the copper slag powder is 200% of the total mass of the all-solid-waste clinker-free cementing material, adding mixing water with the using amount of 40% of the total mass of the all-solid-waste clinker-free cementing material, and continuously stirring for 3 minutes to obtain the conductive mortar of the all-solid-waste clinker-free cementing material, namely the conductive mortar. And (3) operating the S2, the S3 and the S4 at normal temperature.
In the conductive mortar prepared according to the embodiment, the alkali solid waste is used as an alkali activator, the sulfate solid waste is used as a sulfate activator, and alkali-sulfate coupling is used for exciting the solid waste with the pozzolana activity, so that the all-solid-waste clinker-free cementitious material prepared by completely adopting the solid waste material without high-temperature calcination and chemical activating agents is prepared. The caustic sludge is waste material in alkali making industry, the steel slag is a byproduct in steel making process, the red mud is solid waste generated in alumina production process by bauxite, and the caustic sludge, the steel slag and the red mud are alkaline, so the caustic sludge, the steel slag and the red mud are used as alkaline excitants. The desulfurized gypsum is used for absorbing SO in the process of flue gas emission 2 The phosphogypsum is a solid waste produced in a wet-process phosphoric acid process, the fluorgypsum is a byproduct of preparing hydrogen fluoride from sulfuric acid and fluorspar, and the desulfurized gypsum, the phosphogypsum and the fluorgypsum all contain a large amount of calcium sulfate and can be used as a sulfate excitant. Rice hull ash is ash generated by generating electricity or steam and burning rice hulls outdoors, wood ash is residue generated by burning wood and products (wood chips, sawdust and barks) thereof for generating electricity or other purposes, and bagasse ash is a product obtained by burning residue obtained by extracting juice from sugar cane in a sugar making process. Rice hull ash, wood ash, bagasse ash contain a large amount of SiO 2 、A l2 O 3 And Fe 2 O 3 Has volcanic ash activity. The invention adopts alkaline residue, steel slag and red mud as alkaline excitant, uses waste gypsum as sulfate excitant, the waste gypsum can be desulfurized gypsum, phosphogypsum or fluorgypsum, jointly excites slag and biomass ash, the biomass ash can be rice hull ash, wood ash or bagasse ash, the copper slag is granular industrial waste generated by ore in the copper smelting process, although the copper slag can be beneficially reused in the aspects of grinding tool, road construction, ballast and the like, a considerable amount of copper slag is still treated in a refuse landfill, and the copper slag can be used as fine aggregate to replace natural sand. The invention adopts alkaline residue, steel slag and red mud as alkaline excitant, waste gypsum as sulfate excitant and waste gypsumThe clinker-free conductive mortar can be desulfurized gypsum, phosphogypsum or fluorgypsum, slag and high-carbon fly ash are jointly excited, calcium silicate hydrate and ettringite are generated by the slag and the high-carbon fly ash under the double excitation action of alkali and sulfate, the calcium silicate hydrate and the ettringite are used as a full-solid waste clinker-free cementing material, and copper slag with conductive property is doped to prepare the full-solid waste clinker-free conductive mortar. The raw materials used in the invention are all solid waste materials, only the raw materials are required to be dried, ground and screened, chemical reagents and high-temperature calcination are not required, the utilization approach of the solid waste is improved, the product has special application due to the conductivity, and the product is a sustainable material with high added value and environmental friendliness.
The invention relates to a mechanical property experiment of the full-solid waste clinker-free conductive mortar;
the experimental method comprises the following steps: according to the national standard JGJ 70, 0.4 time of water and 2 times of copper slag of powder mass are mixed into a full-solid waste clinker-free cementing material (powder) to prepare mortar, the mixed mortar is put into a bottomed test mould of 70.7mm multiplied by 70.7mm, the test mould is placed in a standard curing box with the temperature of 20 +/-2 ℃ and the relative humidity of more than 90 percent after being vibrated and formed, the test piece is placed in the environment with the temperature of 20 +/-5 ℃ for 24 +/-2 hours after being demoulded, and the compressive strength of the test piece can reach 30MPa by using a cement press when the test piece is cured to the age of 28 days.
Figure BDA0003627892050000141
Figure BDA0003627892050000151
Chart 4
The above graph 4 is: the prepared biomass ash conductive mortar has the resistance and mechanical properties in proportion.
The masses in the above chart 4 are based on the total mass of the cementitious material (the sum of the masses of the caustic sludge, the steel slag, the red mud, the gypsum, the slag and the biomass ash). The results of the graphs show that the slag and the biomass ash generate hydrated calcium silicate gel and ettringite under the double excitation action of alkali-sulfate, so that high-strength and full-solid-waste clinker-free cementing materials can be used for replacing low-grade cement. After the gelled material is mixed with water and copper slag powder, the conductive mortar is obtained, and the conductive mortar has better performance when used as a groove backfill material and a roadbed material.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the appended claims.

Claims (5)

1. A full solid waste clinker-free cementing material is characterized by comprising: the clinker-free cementing material is formed by mixing various solid waste powders, wherein the mixed powder is caustic sludge, steel slag, red mud, waste gypsum, biomass ash and slag; the proportion of each component is 5 to 15 percent of alkaline residue, 5 to 15 percent of steel slag, 5 to 15 percent of red mud, 5 to 25 percent of waste gypsum, 10 to 30 percent of biomass ash and 15 to 65 percent of slag; the waste gypsum is any one of desulfurized gypsum, phosphogypsum and fluorgypsum; the biomass ash is any one of rice hull ash, plant ash, straw ash, wood ash and bagasse ash.
2. A preparation method of a full-solid waste clinker-free cementing material is characterized by comprising the following steps:
step 1, according to the weight parts of 5-15% of alkaline residue, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 10-30% of biomass ash and 15-65% of slag, respectively dehydrating, drying, grinding and screening by a mesh for later use; respectively drying the alkaline residue, the steel slag and the slag at the temperature of 100 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, respectively grinding and sieving through a 325-mesh sieve to respectively obtain alkaline residue powder, steel slag powder and slag powder; drying red mud at the temperature of 100 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, and sieving through a 325-mesh sieve to obtain red mud powder; drying the waste gypsum at the temperature of 50 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, and sieving through a 325-mesh sieve to obtain waste gypsum powder; drying the biomass ash at the temperature of 25 +/-5 ℃ for 0.5 to 1 hour, and naturally cooling to normal temperature;
and 2, fully mixing the alkali slag powder, the steel slag powder, the red mud powder, the waste gypsum powder, the biomass ash powder and the slag powder in a mixer for 3 minutes to uniformly mix the powders, wherein the mixed powder is the full-solid waste clinker-free cementing material.
3. The conductive mortar is characterized by mainly comprising a full-solid waste clinker-free cementing material, copper slag and water; the all-solid-waste clinker-free cementing material comprises alkali slag powder, steel slag powder, red mud, waste gypsum powder, biomass ash and slag powder, wherein the powder comprises 5-15% of alkali slag, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 10-30% of biomass ash and 15-65% of slag; wherein the waste gypsum is any one of desulfurized gypsum, phosphogypsum and fluorgypsum; the biomass ash is any one of rice hull ash, plant ash, straw ash, wood ash and bagasse ash; the copper slag amount is 200-300% of the total mass of the total solid waste clinker-free cementing material, and the water amount is 40-50% of the total mass of the total solid waste clinker-free cementing material; the components of the full-solid waste clinker-free cementing material can be replaced by alkali slag powder, steel slag powder, red mud, waste gypsum powder, high carbon fly ash and slag powder, and the powder proportion is 5-15% of alkali slag, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 15-65% of slag and 10-30% of high carbon fly ash.
4. The preparation method of the conductive mortar is characterized by comprising the following steps:
step 1, respectively drying and dehydrating 5-15% of alkaline residue, 5-15% of steel slag, 5-15% of red mud, 5-25% of waste gypsum, 15-65% of slag and 10-30% of high carbon fly ash in parts by weight, grinding and screening by a mesh sieve for later use; respectively drying the alkaline residue, the steel slag and the slag at the temperature of 100 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, respectively grinding and sieving through a 325-mesh sieve to respectively obtain alkaline residue powder, steel slag powder and slag powder; drying the red mud at the temperature of 100 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, and sieving through a 325-mesh sieve to obtain the red mud; drying the waste gypsum at the temperature of 50 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, and sieving through a 325-mesh sieve to obtain waste gypsum powder; the high carbon fly ash is directly used after being screened by a 325-mesh sieve;
step 2, fully mixing the alkali slag powder, the steel slag powder, the red mud, the waste gypsum powder, the slag powder and the high-carbon fly ash in a mixer for 3 minutes to uniformly mix the powders, wherein the mixed powder is a full-solid waste clinker-free cementing material;
step 3, adding copper slag powder into the clean slurry of the all-solid-waste clinker-free cementing material, adding water accounting for 50% of the total mass of the all-solid-waste clinker-free cementing material, and continuously stirring for 3 minutes to obtain the conductive mortar of the all-solid-waste clinker-free cementing material, namely the conductive mortar; drying the copper slag at the temperature of 100 +/-5 ℃ for 2 hours, naturally cooling to normal temperature, grinding and sieving through a 200-mesh sieve to obtain copper slag powder.
5. The method for preparing the conductive mortar according to claim 4, wherein the method comprises the following steps: replacing the material components in the step 1 with alkaline residue, steel slag, red mud, waste gypsum, biomass ash and slag, and dehydrating, drying, grinding and screening the materials for later use according to the weight parts of 5-15% of the alkaline residue, 5-15% of the steel slag, 5-15% of the red mud, 5-25% of the waste gypsum, 10-30% of the biomass ash and 15-65% of the slag.
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