CN113831033B - Desulfurized fly ash-steel slag composite gelled composition and desulfurized fly ash-steel slag composite gelled material - Google Patents
Desulfurized fly ash-steel slag composite gelled composition and desulfurized fly ash-steel slag composite gelled material Download PDFInfo
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- CN113831033B CN113831033B CN202110871361.3A CN202110871361A CN113831033B CN 113831033 B CN113831033 B CN 113831033B CN 202110871361 A CN202110871361 A CN 202110871361A CN 113831033 B CN113831033 B CN 113831033B
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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
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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
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
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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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
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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
- 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
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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
- 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
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- 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
Abstract
The invention relates to a desulfurized fly ash-steel slag composite gelled composition, a desulfurized fly ash-steel slag composite gelled material and application thereof. The desulfurized fly ash-steel slag composite gelling and gelling composition comprises flue gas desulfurized fly ash, steel slag, a first activating agent and a second activating agent, wherein the first activating agent comprises organic alcohol amine, polycarboxylic acid water reducing agent and optional sulfate, and the second activating agent comprises silica fume. The composite gelling composition of the invention greatly improves the mixing amount of the flue gas desulfurization ash and the steel slag solid waste, especially the sintering flue gas desulfurization ash, in the building materials. The utilization of solid waste resources is realized with low energy consumption, high efficiency and low cost.
Description
Technical Field
The invention relates to the field of industrial solid wastes, in particular to a desulfurized fly ash-steel slag composite gelled composition, a desulfurized fly ash-steel slag composite gelled material and application thereof.
Background
The solid waste production of the bulk industry in China in 2019 is about 36.98 hundred million tons, and the solid waste production is increased by 7.2 percent compared with 34.49 hundred million tons in 2018. Wherein, the metallurgical industry occupies a high proportion of solid wastes, and the main solid wastes are various metallurgical slags, desulfurization byproducts and the like. The balance of ecological environment is not negligible due to the discharge of high-occupancy solid wastes and the existing solid waste inventory, and in recent years, ways for consuming such bulk industrial solid wastes mainly focus on near landfill, soil improvement, valuable element extraction, building material preparation and the like.
Taking a steel plant as an example, the produced solid waste mainly comprises: (1) the method comprises the following steps of (1) desulfurization products generated by flue gas desulfurization treatment in an iron ore sintering section, (2) blast furnace slag generated by water quenching slag treatment in an iron making section, and (3) steel slag generated by slag-making and impurity-removing treatment in a steel making section. Compared with the sintered flue gas desulfurization ash, the resource utilization degree of the blast furnace slag and the steel slag is at a higher level at present, the developed countries can utilize slag discharge in the same year, the utilization rate of the Chinese blast furnace slag also reaches about 80%, the blast furnace slag is mainly used for being doped into concrete to replace cement, the comprehensive utilization rate of the Chinese steel slag is about 30%, and the way of utilizing the steel slag in a large scale is mainly road backfill and preparation of the steel slag cement and a soil conditioner. The main reasons for limiting resource utilization of the sintering flue gas desulfurization ash in the building material field are two reasons: the first is the fluctuation of the components and the second is the CaSO as the main component 3 ·0.5H 2 O has almost no water-hardening property.
The research progress of the comprehensive utilization of the desulfurized fly ash in the prior art mainly focuses on the field of building material preparation, and the desulfurized fly ash is divided into two categories in summary: a pretreatment method and a building material product mixed with other solid waste powder. For example, patent CN201610155138.8 discloses a closed vessel oxidation process for treating sintered flue gas desulfurization ash with MnO 2 As catalyst, hydrogen peroxide or peracetic acid solution as oxidant, stirring in a totally-enclosed oxidation device at 90-100 deg.C for 25-60min, and stopping oxidation modification to obtain CaSO 3 The 0.5h2o content was reduced from 25% to 5% or less. Patent CN201710123453.7 discloses an open container acidic oxidation modification method for treating sintering flue gas desulfurizationAsh, acid auxiliary agent (oxalic acid or dichloroacetic acid or combination of the two) with pKa1 acidity coefficient between that of calcium sulfite and calcium sulfate is used as an oxygen-assisting agent, the oxygen-assisting agent is added into the mixed solution of desulfurized ash and water, oxygen-enriched gas is continuously blown in, and the reaction is carried out in an open reactor for 90-180min at 5 ℃ in the whole process, so that CaSO can be obtained 4 ·2H 2 The O content increased to 94.8%. Patent CN202110065273.4 discloses a complete pretreatment method for resource utilization of desulfurized ash as admixture, which uses (CaSO) 3 +CaSO 4 ) The sintered flue gas desulfurization ash with the content lower than 4% and the activity index higher than 70% is subjected to ball milling for 10min to obtain treated ash with the residue of sieve of 23.9% and the particle size of 45 microns, and the physical and chemical indexes of the sintered flue gas desulfurization ash meet the performance requirements of fly ash of grade II in 'fly ash for cement and concrete' GB/T1596-2017, so that the treated sintered flue gas desulfurization ash can be used for cement and concrete instead of the fly ash of grade II. In addition, the method also discloses a multisource solid-waste coupling hydration hardening mechanism of the screened sintering flue gas desulfurization ash and other solid-waste powder (such as fly ash, slag powder, silica fume and the like) with better activity of volcanic ash so as to improve the activity of the desulfurization ash in the aspect of building material preparation.
Although the prior art realizes the resource treatment of the sintering flue gas desulfurization ash to a certain extent, the prior art still has a plurality of problems. For example, the oxidative pretreatment methods disclosed in CN201610155138.8 and CN201710123453.7 have complicated pre-and post-treatment processes, and the operations of high energy consumption, low efficiency and complicated refinement all bring obstacles for large-scale improvement of the sintering flue gas desulfurization ash. The screening method disclosed in patent CN202110065273.4 is only applicable to the sintering flue gas desulfurization ash with low sulfur content, and under the current environmental protection pressure, the lower requirement of the flue gas emission standard for sulfur content leads to the sulfur content in the sintering flue gas desulfurization ash being generally higher than 20%, so the treatment method is too few in the targeted objects and has no universality. In addition, the mixing amount of the high-sulfur ash compounded with other solid waste powder materials in the concrete cementing material is generally not more than 30%, and the mixing amount of the sintering flue gas desulfurization ash in the composite powder is often less than 15%, namely the mixing amount of the sintering flue gas desulfurization ash in the concrete cementing material is less than 5%, so that the environmental pressure caused by the 2000 ten thousand tons/year discharge amount of the Chinese calcium sulfite type flue gas desulfurization ash is difficult to dissolve with low utilization rate by the method.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a desulfurized fly ash-steel slag composite gelled composition and a desulfurized fly ash-steel slag composite gelled material. The composite gelling composition of the invention greatly improves the mixing amount of the flue gas desulfurization ash and the steel slag solid waste, especially the sintering flue gas desulfurization ash, in the building materials. The utilization of solid waste resources is realized with low energy consumption, high efficiency and low cost.
According to a first aspect of the invention, the invention provides a desulfurization ash-steel slag composite gelling composition, which comprises flue gas desulfurization ash, steel slag, a first activating agent and a second activating agent, wherein the first activating agent comprises organic alcohol amine, polycarboxylic acid water reducing agent and optional sulfate, and the first activating agent comprises silica fume.
According to the invention, the flue gas desulfurization ash and the steel slag are compounded and then added with the corresponding activating agent, and the dissolution of calcium ions in the desulfurization ash and the steel slag can be effectively promoted by utilizing the interaction between the activating agents, so that the early hydration is promoted, meanwhile, the surface structures of the desulfurization ash and the steel slag particles can be damaged, the hydration reaction process is accelerated, and the hydration hardening activity of the flue gas desulfurization ash and the steel slag is obviously improved.
According to some embodiments of the invention, the flue gas desulfurization ash has a mass content of 10% to 50% based on the total mass of the flue gas desulfurization ash and steel slag, such as 12%, 12.5%, 14%, 16%, 18%, 20%, 23%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 37.5%, 39%, 40%, 42%, 44%, 46%, 48%, or a range consisting of any two of these values. The strength of the composite gelled composition is reduced due to the excessively high content of flue gas desulfurization ash; the content is too low, and the utilization rate is too low.
In some embodiments of the present invention, the flue gas desulfurization ash has a mass content of 25% to 45% based on the total mass of the flue gas desulfurization ash and steel slag. In some embodiments, the flue gas desulfurization ash comprises 30-40% by mass of the total mass of the flue gas desulfurization ash and the steel slag.
According to some embodiments of the invention, the steel slag has a mass content of 50% to 90%, for example 88%, 87.5%, 86%, 84%, 82%, 80%, 77%, 73%, 71%, 69%, 67%, 65%, 63%, 62.5%, 61%, 58%, 56%, 54%, 52% or a range consisting of any two of these values, based on the total mass of the flue gas desulfurization ash and the steel slag. In some embodiments of the present invention, the steel slag has a mass content of 55% to 75% based on the total mass of the flue gas desulfurization ash and the steel slag. In some embodiments, the steel slag has a mass content of 60% to 70% based on the total mass of the flue gas desulfurization ash and the steel slag.
According to some embodiments of the invention, the first activator is present in an amount of 0.05% to 0.8% by mass, e.g. 0.1%, 0.25%, 0.3%, 0.45%, 0.5%, 0.65%, 0.7% or a range consisting of any two of these values, based on the total mass of the flue gas desulfurization ash and steel slag. In some embodiments of the present invention, the first activator is present in an amount of 0.2 to 0.6% by mass based on the total mass of the flue gas desulfurization ash and the steel slag. In some embodiments, the first activator is present in an amount of 0.2% to 0.4% by mass based on the total mass of the flue gas desulfurization ash and steel slag.
According to some embodiments of the invention, the second activator is present in an amount of 0.3% to 1.5% by mass, such as 0.4%, 0.6%, 0.7%, 0.8%, 0.9%, 0.95%, 1.0%, 1.05%, 1.3%, 1.4% or a range consisting of any two of these values. In some embodiments of the present invention, the second activator is present in an amount of 0.5% to 1.2% by mass based on the total mass of the flue gas desulfurization ash and the steel slag. In some embodiments, the second activator is present in an amount of 0.8% to 1.1% by mass, based on the total mass of the flue gas desulfurization ash and steel slag.
The first activating agent can effectively promote early hydration and accelerate the hydration reaction process. The second activating agent is beneficial to the increase of the hydration duration and the later mechanical property. According to the invention, the hydration hardening activity of the material is effectively improved through the synergistic effect between the first activating agent and the second activating agent.
According to some embodiments of the invention, the organic alcohol amine is present in an amount of 50% to 75% by mass, for example 53%, 58%, 60%, 62%, 64%, 67%, 69%, 70%, 73% or a range consisting of any two of these values, based on the total mass of the first activator. In some embodiments, the organic alcohol amine is present in an amount of 55% to 65% by mass, based on the total mass of the first activator.
According to some embodiments of the invention, the sulfate salt is present in an amount of 5% to 20% by mass, e.g. 7%, 9%, 10%, 12%, 14%, 16%, 18% by mass or a range consisting of any two of these values, based on the total mass of the first activator. In some implementations, the sulfate is present in an amount of 10% to 15% by mass of the total mass of the first activator.
According to some embodiments of the present invention, the polycarboxylate water reducer has a mass content of 20% to 35% by mass of the total mass of the first activator, for example, in the range of 22%, 24%, 26%, 28%, 32%, 34% or any two of these values, and in some embodiments, the polycarboxylate water reducer has a mass content of 25% to 30% by mass of the total mass of the first activator.
The components of the first activating agent interact with each other, so that the early hydration of the compounded flue gas desulfurization ash and steel slag can be effectively promoted, and the hydration reaction process can be accelerated.
According to some embodiments of the invention, the organic alcohol amine is selected from one or more of monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine. In some embodiments, the organic alcohol amine is selected from two of monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine, such as monoethanolamine and diethanolamine, diethanolamine and triethanolamine, triethanolamine and triisopropanolamine, monoethanolamine and triethanolamine.
According to some embodiments of the invention, the organic alcohol amine is triethanolamine and triisopropanolamine, wherein the triethanolamine is present in an amount of 10% to 30% by mass, for example, 7%, 9%, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 26%, 28% or a range consisting of any two of these values, based on the total mass of the first activator; the triisopropanolamine is present in an amount of 40% to 60% by mass, for example, in a range of 41%, 43%, 45%, 47%, 49%, 52%, 54%, 56%, 58% or any two of these values.
In some embodiments of the invention, the organic alcohol amine is triethanolamine and triisopropanolamine, wherein the triethanolamine is present in an amount of 13 to 25% by mass and the triisopropanolamine is present in an amount of 40 to 50% by mass, based on the total mass of the first activator.
According to some embodiments of the present invention, the desulfurized fly ash-steel slag composite gelled composition of the present invention is composed of flue gas desulfurized fly ash, steel slag, a first activating agent and a second activating agent, wherein the first activating agent is organic alcohol amine, sulfate and polycarboxylic acid water reducing agent, and the second activating agent is silica fume.
In some embodiments, the desulfurization ash-steel slag composite cementing composition consists of flue gas desulfurization ash, steel slag, a first activating agent and a second activating agent, wherein the first activating agent is triethanolamine, triisopropanolamine and a polycarboxylic acid water reducing agent, and the second activating agent is silica fume.
In some embodiments, the desulfurized fly ash-steel slag composite cementitious composition of the invention is composed of flue gas desulfurized fly ash, steel slag, a first activating agent and a second activating agent, wherein the first activating agent is triethanolamine, triisopropanolamine, sulfate and a polycarboxylic acid water reducing agent, and the second activating agent is silica fume.
In some embodiments, the first activator is triethanolamine, triisopropanolamine, sulfate, and a polycarboxylic acid water reducer, and the triethanolamine comprises 14% to 20% by mass, the triisopropanolamine comprises 40% to 50% by mass, the sulfate comprises 10% to 15% by mass, and the polycarboxylic acid water reducer comprises 25% to 30% by mass, based on the total mass of the first activator.
According to some embodiments of the invention, the flue gas desulfurization ash is selected from flue gas desulfurization ash produced by a dry flue gas desulfurization process or a semi-dry flue gas desulfurization process. In some embodiments, the calcium sulfite content in the flue gas desulfurization ash is 10% to 60% by mass. In some embodiments, the flue gas desulfurization ash is desulfurization ash obtained after dry or semi-dry desulfurization of flue gas in an iron ore sintering section of a steel plant.
According to some embodiments of the invention, the flue gas desulfurization ash comprises 50-70wt% CaO, 5-30wt% SO 3 、0.5wt％-3.0wt％Cl、0.5wt％-2.0wt％Na 2 O、1.0wt％-3.0wt％SiO 2 、0.5wt％-1.0wt％Al 2 O 3 、0.1wt％-1.0wt％Fe 2 O 3 0-1.0wt% of MgO and 0-0.3wt% of K 2 O。
According to some embodiments of the invention, the steel slag comprises 20wt% -45wt% CaO, 5wt% -35wt% Fe 2 O 3 、10wt％-20wt％SiO 2 、5wt％-10wt％MgO、1.0wt％-4.0wt％MnO、0.5wt％-2.5wt％P 2 O 5 、1.0wt％-8.0wt％Al 2 O 3 、0-2.0wt％TiO 2 And 0-1.0wt% of Cr 2 O 3 。
According to some embodiments of the invention, the steel slag is steel slag powder, preferably the steel slag powder has an average particle size of 0.1 μm to 50 μm.
According to some embodiments of the invention, the sulfate is selected from one or more of alkali metal sulfates. In some embodiments, the sulfate salt is sodium sulfate and/or potassium sulfate.
The polycarboxylate superplasticizer is a polycarboxylate superplasticizer which is conventionally adopted in the field. In some embodiments of the invention, the polycarboxylate water reducer is a "high performance water reducer" as specified in the national standard GB 8076-2008 "concrete admixture".
According to a second aspect of the present invention, the present invention provides a desulfurized fly ash-steel slag powder composite cementitious material, which comprises the desulfurized fly ash-steel slag powder composite cementitious composition of the first aspect and water.
According to some embodiments of the invention, the ratio of the mass of water to the total mass of the flue gas desulfurization ash and steel slag is 0.3 to 0.5. The water consumption is too small, the workability is poor, and the construction cannot be carried out; large water consumption, and evaporation of a large amount of free water after hydration, resulting in poor strength.
According to a third aspect of the present invention, there is provided the use of the desulfurized fly ash-steel slag powder composite cementitious composition of the first aspect or the desulfurized fly ash-steel slag powder composite cementitious material of the second aspect in building materials, particularly in concrete or mortar.
According to some embodiments of the present invention, the desulfurized fly ash-steel slag powder composite cementitious composition or cementitious material of the present invention can be used for preparing building materials such as mortar, baking-free bricks, pervious concrete or concrete prefabricated parts. In some embodiments, when the 28-day compressive strength requirement of the building material is less than 30MPa, the desulfurized fly ash-steel slag powder composite cementitious composition or cementitious material of the present invention can be used in the building material alone. When the 28-day compressive strength requirement of the building material is higher than 30MPa, the desulfurized fly ash-steel slag powder composite gelled composition or gelled material can be compounded with cement for use.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention completely replaces various oxidation treatment technologies, and does not need to use oxidation products CaSO 4 ·2H 2 The hydration hardening characteristic of O realizes resource utilization, the pretreatment method mentioned in the prior art is skipped, and the sintered flue gas desulfurization ash-steel slag powder composite micro powder and the activating agent are directly combined for use at the terminal of preparing the building material, so that the activity is improved, and the energy consumption is lower, the efficiency is high and the cost is lower.
2. The invention is suitable for resource utilization of various sintering flue gas desulfurization ashes with different sulfur contents, and the low-aluminum steel slag powder is introduced into a high-sulfur system to be compounded with the high-sulfur steel slag powder to form composite micro powder, so that the generation of ettringite which is easy to cause volume expansion in a hydration product can be ensured at first, and therefore, the sintering flue gas desulfurization ashes do not need to be divided according to the sulfur content, and the method is simple and easy to implement, so that the use amount of the sintering flue gas desulfurization ashes in building materials can be further increased. And secondly, the two kinds of powder are solid wastes of the steel plant, the source is convenient, and the cost is low, so that the invention provides a reproducible solid waste treatment technical path for the steel plant.
3. The invention effectively improves the hydration and hardening activity of the desulfurized fly ash by the specific activating agent suitable for the sintered flue gas desulfurized fly ash-steel slag powder composite micro powder, not only can realize that the sintered flue gas desulfurized fly ash-steel slag powder composite powder is utilized in building material preparation in a larger mixing amount, but also can even realize the mixing proportion design of the all-solid waste rubber material of the building material with the requirement of 28 days compressive strength below 30 MPa.
Drawings
FIG. 1 is a particle size distribution and SEM image of sintered flue gas desulfurization ash and steel slag powder used in the embodiment of the present invention;
FIG. 2 is an XRD pattern of the sintered flue gas desulfurization ash and steel slag powder employed in the examples of the present invention;
FIG. 3 is an XRD pattern of 14 days hydration of samples of comparative example 3, example 1, example 3 of the present invention;
fig. 4 is an SEM image of samples of comparative example 3, example 1, and example 3 of the present invention hydrated for 14 days.
Detailed Description
The invention is further illustrated by the following examples, but it is to be noted that the scope of the invention is not limited thereto, but is defined by the claims.
It should be particularly noted that two or more aspects (or embodiments) disclosed in the context of the present specification may be combined with each other at will, and thus form part of the original disclosure of the specification, and also fall within the scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
Starting materials
(1) Sintering flue gas Desulfurization Ash (DA): the sintering flue gas desulfurization ash used in the invention is solid waste collected after flue gas desulfurization treatment in iron ore sintering section of steel plant, wherein the desulfurization method adopts dry method/semi-dry method desulfurization process, and the specific process is' in-furnace calcium spraying-tail humidifying desulfurization process". The sintering flue gas desulfurization ash used in the present invention has not been subjected to any treatment, wherein CaSO 3 The mass content of (A) is 52.6%; the macro morphology is white gray powder; the micro-morphology is shown in figure 1 and is porous loose irregular spherical particles; d 50 =3.65 μm, particle size distribution as shown in fig. 1; the main oxide compositions are XRF measured as shown in Table 1, and mainly CaO and SO 3 And the like. The major mineral phases were determined by XRD as shown in FIG. 2 and were predominantly CaSO 3 ·0.5H 2 O、CaSO 4 ·2H 2 O、CaCO 3 And the like.
(2) Steel slag powder (SS): the steel slag powder used in the invention is steel slag generated during slagging and impurity removal in a steel-making section of a steel plant, and the steel-making process is a converter steel-making process. The steel slag powder used in the invention is obtained by grinding the steel slag, and the macroscopic appearance of the steel slag powder is brown powder; the micro-morphology is shown in figure 1, and is relatively dense irregular blocky particles; d 50 =5.51 μm, particle size distribution as shown in fig. 1; the main oxide compositions are shown in Table 1 by XRF measurements and are mainly CaO and Fe 2 O 3 、SiO 2 MgO, and the like. The main mineral phase is measured by XRD and is shown as C in figure 2 2 S、C 3 S, RO phase, C 12 A 7 、C 4 AF、C 2 F and the like.
TABLE 1 chemical composition of sintering flue gas desulfurization ash and steel slag powder
(3) Activating agent: the activating agent is composed of a first activating agent and a second activating agent.
A first activating agent: the water reducing agent is prepared by uniformly mixing and stirring triethanolamine, triisopropanolamine, anhydrous sodium sulfate and polycarboxylic acid water reducing agent (solid), and the specific mass percentage of each component is shown in table 3. Wherein the triethanolamine, the triisopropanolamine and the anhydrous sodium sulfate are all of industrial purity, and the water reducing rate of the polycarboxylic acid water reducing agent (BASF model: RHEOPLUS 416) is 20-40%.
A second activating agent: silicon ash (solid waste produced by industrial smelting, which is volatilized by ferroalloy when ferrosilicon is smeltedSiO of hair 2 And Si gas is oxidized and condensed rapidly in air when discharged), wherein SiO is 2 The content is 90-98%.
(4) Water: the water used in the invention is tap water or industrial water.
Preparation method
Firstly, a part of the mixing water is used for fully dissolving the first activating agent, then the first activating agent and the second activating agent are mixed with the sintering flue gas desulfurization ash and the steel slag powder, and the rest mixing water is added for mixing. Wherein the first activating agent is added by an external mixing method, and the second activating agent B is added by an internal mixing method.
Examples and comparative examples
1. Experiment of hydration hardening activity of desulfurized fly ash-steel slag composite cementing material
The section relates to 7 comparative examples and 17 examples, and the hydration hardening activity of the cement is evaluated by the compressive strength of 3/7/14/28 days, wherein the comparative example 1 is the pure sintering flue gas desulfurization ash hydration hardening, the comparative example 2 is the pure steel slag powder hydration hardening, and the comparative example 3 is the pure sintering flue gas desulfurization ash. Comparative examples 4 and 5 are hydration hardening of pure sintering flue gas desulfurization ash and pure steel slag powder under the condition of using an activator respectively. Comparative examples 6 and 7 are hydration hardening in the case of using the first activator a and the second activator B alone, respectively. Examples 1 to 17 show the hydration hardening of different proportions of activators and amounts of activators in the case of different proportions of the pure sintered flue gas desulfurization ash and steel slag powder.
The specific test method comprises the following steps: the weighed sintering flue gas desulfurization ash, steel slag powder, activating agent and water are stirred into fresh slurry, and the stirring process is carried out according to 'stirring of cement pure slurry' in GB/T1346-2011 'inspection method for water consumption, setting time and stability of cement standard consistency'. The stirred fresh slurry is introduced into a steel mould for forming (test block specification: 40mm multiplied by 40 mm), demoulding is carried out after 24 hours, the mould is placed in the air curing condition at room temperature after demoulding, the compression strength is tested by using a servo press machine when 3 days, 7 days, 14 days and 28 days respectively start from the preparation day, and the load loading speed is 500N/s.
TABLE 2 proportions and Properties of the ingredients of the cementitious materials of the examples and comparative examples
TABLE 3 proportions of the respective components of the activators corresponding to the examples and comparative examples
The hydration products of comparative example 3, example 1 and example 3 were investigated by XRD and SEM tests, and the results showed that the hydration products of the cement systems of examples 1 and 3 according to the invention had no ettringite formation which caused volume expansion, al was present in the form of N-A-S-H, C-A-S-H, and some CaSO was present in the form of CaSO 3 ·0.5H 2 Oxidizing and hydrating O with CaSO 4 ·2H 2 O exists in the form of, and part of sulfur exists in unhydrated CaSO 3 ·0.5H 2 And (4) in O. It is also evident from the SEM photographs that the hydrated product is rich and the structure is dense in examples 1 and 3, and the boundaries of the particles of the raw material in comparative example 3 are also clear and the degree of hydration is low.
2. Experiment for improving hydration hardening activity of desulfurized fly ash-steel slag composite cementing material partially replacing cement
Example 18 is a hydration hardening test using an activator in which 50% of cement is replaced with a different blend of desulfurized fly ash and steel slag powder, and the hydration hardening activity of the test is evaluated at a compressive strength of 3/7/14 days.
The specific test method comprises the following steps: the weighed sintering flue gas desulfurization ash, steel slag powder, activator, cement and water are stirred into fresh slurry, and the stirring process is carried out according to the stirring of cement pure slurry in GB/T1346-2011 'test method for water consumption, setting time and stability of cement standard consistency'. The stirred fresh slurry is introduced into a steel mould for forming (test block specification: 40mm multiplied by 40 mm), demoulding is carried out after 24 hours, the mould is placed in the room-temperature air curing condition after demoulding, the compression strength is tested by using a servo press machine when 3 days, 7 days, 14 days and 28 days are carried out respectively from the preparation day, and the load loading speed is 500N/s.
Table 4 shows the proportions of the components in the examples
Table 5 concrete proportions of activators
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (12)
1. The desulfurized fly ash-steel slag composite gelled composition comprises flue gas desulfurized fly ash, steel slag, a first activating agent and a second activating agent, wherein the first activating agent comprises organic alcohol amine, polycarboxylic acid water reducing agent and sulfate, the second activating agent comprises silica fume, the mass content of calcium sulfite in the flue gas desulfurized fly ash is 10-60%,
based on the total mass of the flue gas desulfurization ash and the steel slag, the mass content of the flue gas desulfurization ash is 30-50%, the mass content of the first activator is 0.2-0.6%, the mass content of the second activator is 0.8-1.2%,
the organic alcohol amine is triethanolamine and triisopropanolamine, and based on the total mass of the first activator, the mass content of the triethanolamine is 10-20%, the mass content of the triisopropanolamine is 40-50%, the mass content of the sulfate is 10-15%, and the mass content of the polycarboxylic acid water reducing agent is 25-30%.
2. The composition of claim 1, wherein the flue gas desulfurization ash comprises 30-40% by mass of the total mass of the flue gas desulfurization ash and the steel slag;
and/or the steel slag has a mass content of 50-70%.
3. The composition of claim 1, wherein the steel slag has a mass content of 60 to 70% based on the total mass of the flue gas desulfurization ash and the steel slag.
4. The composition of claim 1 or 2, wherein the first activator is present in an amount of 0.2 to 0.4% by mass based on the total mass of the flue gas desulfurization ash and the steel slag;
and/or the mass content of the second activating agent is 0.8-1.1%.
5. The composition according to any one of claims 1 to 3, wherein the flue gas desulfurization ash is selected from flue gas desulfurization ash produced by a dry flue gas desulfurization process or a semi-dry flue gas desulfurization process.
6. The composition as claimed in claim 5, wherein the flue gas desulfurization ash is the desulfurization ash after dry or semi-dry desulfurization of flue gas in iron ore sintering section of steel plant.
7. A composition according to any of claims 1 to 3, characterized in that the sulphate is selected from one or more of the alkali metal sulphates.
8. The composition of claim 7, wherein the sulfate is sodium sulfate and/or potassium sulfate.
9. A desulphurised ash-steel slag composite cementitious material comprising a desulphurised ash-steel slag composite cementitious composition according to any one of claims 1 to 8 and water.
10. Cement according to claim 9, characterised in that the ratio of the mass of water to the total mass of flue gas desulphurisation ash and steel slag is 0.3-0.5.
11. Use of the desulphurised ash-steel slag composite cementitious composition according to any one of claims 1 to 8 or the desulphurised ash-steel slag composite cementitious material according to claim 9 or 10 in construction materials.
12. Use according to claim 11, characterized in that it is in concrete or mortar.
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