CN117447105A - Waste concrete composite phosphogypsum-based electrochemical synthesized cement and preparation method thereof - Google Patents
Waste concrete composite phosphogypsum-based electrochemical synthesized cement and preparation method thereof Download PDFInfo
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- CN117447105A CN117447105A CN202311502561.7A CN202311502561A CN117447105A CN 117447105 A CN117447105 A CN 117447105A CN 202311502561 A CN202311502561 A CN 202311502561A CN 117447105 A CN117447105 A CN 117447105A
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- 239000002699 waste material Substances 0.000 title claims abstract description 96
- 239000004567 concrete Substances 0.000 title claims abstract description 86
- 239000004568 cement Substances 0.000 title claims abstract description 80
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 19
- 239000002689 soil Substances 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical group [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
Classifications
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
-
- 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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses waste concrete composite phosphogypsum-based electrochemical synthetic cement and a preparation method thereof, wherein the preparation method comprises the following steps: s1: pretreating the waste concrete to obtain waste concrete with target granularity; s2: adding water into the waste concrete, and uniformly stirring to obtain waste concrete slurry; s3: electrolyzing the waste concrete slurry, and collecting carbon dioxide and electrolysis products generated by electrolysis; s4: adding water, waste soil and phosphogypsum into the electrolysis product, uniformly stirring, and regulating pH to be acidic to obtain calcium ion slurry; s5: heating the calcium ion slurry under the stirring condition, stopping stirring and heating after the calcium ion slurry is completely converted into cement, naturally cooling and curing to obtain cement clinker; s6: and grinding and packaging the cement clinker to obtain the waste concrete composite phosphogypsum-based electrochemical synthesized cement. The invention can prepare cement with excellent performance at a lower temperature, and greatly reduces energy consumption.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to waste concrete composite phosphogypsum-based electrochemical synthetic cement and a preparation method thereof.
Background
The waste concrete is the main solid waste generated after the service life of the concrete is reached and the concrete is removed, and the waste concrete accounts for 60 to 70 percent of the total amount of the solid waste of the building. It is estimated that China produces about 6×10 per year 8 t waste concrete. Phosphogypsum is a byproduct generated in the wet-process phosphoric acid production process, and about 4-5 t phosphogypsum is generated per 1t phosphoric acid produced. Therefore, the recycling of phosphogypsum becomes a primary task of the phosphate fertilizer industry.
The cement industry is an energy-intensive industry, and energy consumption and carbon emission respectively account for 12% -15% and 5% -7% of the total global value. The traditional cement production process not only consumes a large amount of fossil energy, but also can generate a large amount of greenhouse gases and SO 2 And the like. In order to reduce the energy consumption and carbon emissions of cement production processes, fundamental changes to conventional cement calcination techniques are required.
Disclosure of Invention
The invention aims to provide the waste concrete composite phosphogypsum-based electrochemical synthesized cement and the preparation method thereof.
The technical scheme of the invention is as follows:
in one aspect, a method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement is provided, which comprises the following steps:
s1: pretreating the waste concrete to obtain waste concrete with target granularity;
s2: adding water into the waste concrete, and uniformly stirring to obtain waste concrete slurry;
s3: placing the waste concrete slurry into an electrochemical reaction container for electrolysis, and collecting carbon dioxide and electrolysis products generated by the electrolysis;
s4: adding water, waste soil and phosphogypsum into the electrolysis product, uniformly stirring, and regulating pH to be acidic to obtain calcium ion slurry;
s5: heating the calcium ion slurry under the stirring condition, stopping stirring and heating after the calcium ion slurry is completely converted into cement, naturally cooling and curing to obtain cement clinker;
s6: and grinding and packaging the cement clinker to obtain the waste concrete composite phosphogypsum-based electrochemical synthesized cement.
Preferably, in step S1, the pretreatment includes crushing, washing and sieving.
Preferably, in step S1, the target particle size is 0.2-1.5mm.
Preferably, in the step S2, the concentration of the waste concrete slurry is 0.1-3.2mol/L.
Preferably, in step S3, the electrolysis is performed at a voltage of 220V and a current density of 800-2000A/m 3 The reaction temperature is 30-105 ℃ and the reaction time is 30-60min.
Preferably, in the step S4, the amount of the electrolysis product is 50-70% by weight, the amount of the waste soil is 20-30% by weight, the amount of the phosphogypsum is 10-25% by weight, and the balance is water.
Preferably, in step S4, the pH of the calcium ion slurry is 4 to 7.
Preferably, in step S4, sulfuric acid is used to adjust the pH.
Preferably, in the step S5, the stirring speed of the stirring condition is 50-80rad/min; when heating, heating is performed under normal pressure, and the heating temperature is 90-250 ℃.
On the other hand, the invention also provides the waste concrete composite phosphogypsum-based electrochemical synthetic cement prepared by adopting any one of the preparation methods.
The beneficial effects of the invention are as follows:
1. the invention can be produced at low temperature and normal pressure, and has good safety and portability; the production process does not need extreme equipment conditions such as high temperature, high pressure and the like, so that the energy consumption and the equipment loss can be greatly reduced, and the cost is saved.
2. Compared with the kiln mode of the traditional cement production, the kiln calcination process is omitted, and is just CO 2 A large amount of discharge process; the invention uses the electrochemical method to replace kiln calcination, uses electric energy to replace fuel combustion, has higher energy utilization efficiency, saves energy and greatly reduces carbon emission; in addition, the invention has lower pollution treatment cost, lower transportation cost and higher production efficiency, can bring greater profit to cement manufacturers and has good economic benefit.
3. The invention does not need to use harmful chemical reagents, does not generate pollutants, avoids the influence of waste and waste residues generated by high-temperature firing on the environment, and greatly improves the environment-friendly property.
4. CO produced in the production process of the invention 2 Can be converted into valuable carbonaceous products such as carbon monoxide, methane, methanol and the like in an in-situ conversion or storage delivery chemical plant, realizes zero emission and simultaneously realizes effective utilization of resources.
5. The invention has simple process, low implementation difficulty, flexible production and large-scale production; the device modular design and production can be carried out according to market demands, the production scale and the product types can be adjusted, and the device has stronger production flexibility; an automatic control system and mechanical equipment can be adopted to realize continuous and automatic production, and the degree of automation is high; the production process is more controllable, the utilization rate of raw materials is high, and the overall quality is more uniform; short production period, high reaction speed and high production efficiency.
6. The invention can produce cement on site, does not need a large amount of raw material transportation and finished product transportation, and reduces the cost, energy consumption and environmental impact caused by long-distance transportation.
7. The invention can adopt a closed production system, and can avoid personnel contacting dangerous environments; by adopting the automatic control system and the safety protection equipment, the risks of manual operation errors and accidents can be reduced, and the production safety is higher.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement;
FIG. 2 is a schematic view of the electrolytic mechanism of the method for preparing the waste concrete composite phosphogypsum-based electrochemical synthetic cement.
Detailed Description
The invention will be further described with reference to the drawings and examples. It should be noted that, without conflict, the embodiments and technical features of the embodiments in the present application may be combined with each other. It is noted that all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs unless otherwise indicated. The use of the terms "comprising" or "includes" and the like in this disclosure is intended to cover a member or article listed after that term and equivalents thereof without precluding other members or articles.
On the one hand, as shown in fig. 1, the invention provides a preparation method of waste concrete composite phosphogypsum-based electrochemical synthetic cement, which comprises the following steps:
s1: and (3) pretreating the waste concrete to obtain the waste concrete with the target granularity.
In a specific embodiment, the pretreatment includes crushing, washing, and sieving, and the target particle size is 0.2-1.5mm. And when the granularity of the waste concrete subjected to primary pretreatment does not reach the target granularity, repeating the pretreatment step until the target granularity is reached. When the waste concrete is washed, impurities and harmful substances in the waste concrete can be washed and removed.
In the above embodiment, the target particle size is set to 0.2-1.5mm, which can avoid the problems that the particle size is too fine to increase the specific surface area of the raw materials, the energy consumption and the cost are increased, the reaction is not thorough due to the too large particle size, the raw materials are wasted, and the quality of the cement product is affected.
In a specific embodiment, the waste concrete has the main chemical composition: 34-46% CaCO 3 、16-28％CaSiO 3 、10-15％ Ca(OH) 2 、10-23％ SiO 2 、10-18％ CaAl 2 Si 2 O 3 、2-6％ Ca 5 Si 6 O 16 (OH)·4H 2 O, loss on ignition is 35-42%.
S2: and adding water into the waste concrete, and uniformly stirring to obtain waste concrete slurry.
In a specific embodiment, when water is added to the waste concrete, the water used is deionized water, which can prevent other ions from being generated during the subsequent electrolysis. When water is added, water is added under stirring, and the stirring speed and time are controlled so that waste concrete slurry with good wettability and uniformity is obtained.
In a specific embodiment, the concentration of the waste concrete slurry is 0.1-3.2mol/L. In the embodiment, the concentration of the waste concrete slurry is set to be 0.1-3.2mol/L, so that the influence of excessive or insufficient slurry concentration and consistency on the subsequent electrolysis effect can be avoided.
S3: and placing the waste concrete slurry into an electrochemical reaction container for electrolysis, and collecting carbon dioxide and electrolysis products generated by the electrolysis.
In a specific embodiment, the electrolysis is carried out using a voltage of 220V and a current density of 800-2000A/m 3 The reaction temperature is 30-105 ℃ and the reaction time is 30-60min.
As shown in fig. 2, when electrolysis is performed, the following reactions are included:
2H + +CO 3 2- →CO 2 ↑+H 2 O (2)
Ca + +2OH - →Ca(OH) 2 (3)
Mg 2+ +2OH - →Mg(OH) 2 (4)
Fe 3+ +3OH - →Fe(OH) 3 (5)
Al 3+ +3OH - →Al(OH) 3 (6)
the electrolytic product obtained comprises a high amount of Ca (OH) because of the high content of calcium-containing compounds and the low content of other ionic compounds in the waste concrete 2 Part of Al (OH) 3 And SiO 2 Small amount of Fe (OH) 3 And Mg (OH) 2 I.e. the electrolysis product is in Ca (OH) 2 A composition based on the above.
It should be noted that the electrolytic product is in a liquid state or a semi-solid state, so that the subsequent steps are immediately performed after the electrolytic product is obtained, and the agglomeration and the advanced curing of the product due to the evaporation of water are avoided, thereby affecting the cement quality.
S4: and adding water, waste soil and phosphogypsum into the electrolysis product, uniformly stirring, and regulating pH to be acidic to obtain calcium ion slurry.
In a specific embodiment, the electrolysis product is used in an amount of 50-70% by weight, the waste soil is used in an amount of 20-30% by weight, the phosphogypsum is used in an amount of 10-25% by weight, and the balance is water.
In a specific embodiment, the main components of the spoil are: 42-55% SiO 2 19-30% free water, 19-24% Al 2 O 3 、1-3.5％ Fe 2 O 3 、0.7-1.2％ TiO 2 The loss on ignition is 9-14%; the main components of the phosphogypsum are as follows: 65-76% CaSO 4 ·2H 2 O, 18-30% free water, 3-6%H 3 PO 4 1-2% fluorine, 1-3% insoluble residue, loss on ignition: 10-30％。
In a specific embodiment, sulfuric acid is used to adjust the pH of the calcium ion slurry to a pH of 4-7. In this example, by adjusting the pH with sulfuric acid, it can be avoided that the cement product quality is affected; by adjusting the calcium ion slurry to be acidic, it can promote dissolution and reaction of calcium ions and other auxiliary components; and by adjusting the pH of the calcium ion slurry to 4-7, it can avoid problems that the pH is too low, calcium ions are difficult to dissolve, the reaction is hindered, and the pH is too high, possibly causing other reactions.
S5: and heating the calcium ion slurry under the stirring condition, stopping stirring and heating after the calcium ion slurry is completely converted into cement, naturally cooling and curing to obtain cement clinker.
In a specific embodiment, the stirring conditions are such that the stirring rate is 50-80rad/min; when heating, heating is performed under normal pressure, and the heating temperature is 90-250 ℃.
S6: and grinding and packaging the cement clinker to obtain the waste concrete composite phosphogypsum-based electrochemical synthesized cement.
On the other hand, the invention also provides the waste concrete composite phosphogypsum-based electrochemical synthetic cement prepared by adopting any one of the preparation methods.
Example 1
The invention relates to waste concrete composite phosphogypsum-based electrochemical synthesized cement, which is prepared by adopting the preparation method of the waste concrete composite phosphogypsum-based electrochemical synthesized cement. In this example, the proportions of the raw materials are shown in table 1:
TABLE 1 raw material proportions
| Waste concrete | Waste soil | Phosphogypsum | Water and its preparation method |
| 55kg | 30kg | 15kg | 25kg |
The relevant parameter settings for each step are shown in table 2:
TABLE 2 reaction parameters
Mineral content C of the obtained waste concrete composite phosphogypsum-based electrochemical synthesized cement 3 S、C 2 S、C 3 A、C 4 AF was 45.34%, 23.88%, 14.81%, 10.86%, respectively. The cement index test results are shown in table 3:
TABLE 3 Cement index test results
In Table 3, KH represents the saturation coefficient of lime, which means SiO in cement clinker 2 The degree of saturation with CaO to tricalcium silicate; SM represents silicon rate, which means SiO in cement clinker 2 With Al 2 O 3 、Fe 2 O 3 The ratio of the sums; IM represents Al in clinker 2 O 3 With Fe 2 O 3 Is a ratio of C in clinker 3 A and C 4 The relative amounts of AF; s represents the calcium-silicon ratio of the cement clinker.
Example 2
The invention relates to waste concrete composite phosphogypsum-based electrochemical synthesized cement, which is prepared by adopting the preparation method of the waste concrete composite phosphogypsum-based electrochemical synthesized cement. In this example, the proportions of the raw materials are shown in table 4:
TABLE 4 raw material proportions
| Waste concrete | Waste soil | Phosphogypsum | Water and its preparation method |
| 60kg | 25kg | 15kg | 25kg |
The relevant parameter settings for each step are shown in table 5:
TABLE 5 reaction parameters
Mineral content C of the obtained waste concrete composite phosphogypsum-based electrochemical synthesized cement 3 S、C 2 S、C 3 A、C 4 AF was 47.23%, 21.56%, 12.77% and 9.25% respectively. The cement index test results are shown in table 6:
TABLE 6 Cement index test results
Example 3
The invention relates to waste concrete composite phosphogypsum-based electrochemical synthesized cement, which is prepared by adopting the preparation method of the waste concrete composite phosphogypsum-based electrochemical synthesized cement. In this example, the proportions of the raw materials are shown in table 7:
TABLE 7 raw material formulation
| Waste concrete | Waste soil | Phosphogypsum | Water and its preparation method |
| 70kg | 20kg | 10kg | 25kg |
The relevant parameter settings for each step are shown in table 8:
TABLE 8 reaction parameters
Mineral content C of the obtained waste concrete composite phosphogypsum-based electrochemical synthesized cement 3 S、C 2 S、C 3 A、C 4 AF was 51.42%, 23.45%, 12.36%, 8.99% and the conversion was 91.3%, respectively. The cement index test results are shown in table 9:
TABLE 9 Cement index test results
Example 4
Unlike example 3, the target particle size in step S1 of this example was 0.5mm, the concentration of the waste concrete slurry in step S2 was 2.5mol/L, and the reaction time used for the electrolysis in step S3 of this example was 46min. The conversion rate of the waste concrete composite phosphogypsum-based electrochemical synthetic cement obtained in the embodiment is 92.5%, C 3 S and C 2 The sum of the S contents was 75.67%.
Example 5
Unlike example 3, the target particle size in step S1 of this example was 1mm, the concentration of the waste concrete slurry in step S2 was 2.5mol/L, and the reaction time used for the electrolysis in step S3 of this example was 50min. The conversion rate of the waste concrete composite phosphogypsum-based electrochemical synthetic cement obtained in the embodiment is 90.8%, C 3 S and C 2 The sum of the S content is 73.79%.
Example 6
Unlike example 3, the reaction temperature used in the electrolysis in step S3 of this example was 80℃and the reaction time was 40min. The conversion rate of the waste concrete composite phosphogypsum-based electrochemical synthetic cement obtained in the embodiment is 91.7%, C 3 S and C 2 The sum of the S content is 75.16%.
Example 7
Unlike example 3, the current density used in the electrolysis in step S3 of this example was 1200A/m 3 The reaction temperature is 80 ℃ and the reaction time is 38min. The conversion rate of the waste concrete composite phosphogypsum-based electrochemical synthetic cement obtained in the embodiment is 92.9%, C 3 S and C 2 The sum of the S content is 75.50%.
Example 8
Unlike example 3, the heating temperature used in step S5 of this example was 110 ℃. Mineral content C of the waste concrete composite phosphogypsum-based electrochemical synthetic cement obtained in the embodiment 3 S、C 2 S、C 3 A、C 4 AF was 51.36%, 23.65%, 12.24% and 8.89%, respectively.
Example 9
Unlike example 3, the pH of step S4 of this example was 6 and the heating temperature used in step S5 was 110 ℃. Mineral content C of the waste concrete composite phosphogypsum-based electrochemical synthetic cement obtained in the embodiment 3 S、C 2 S、C 3 A、C 4 AF was 50.03%, 21.78%, 11.97% and 8.58%, respectively.
Analysis of the results of the above examples shows that:
(1) Particle size and concentration influence mineral composition mainly by influencing the electrolytic conversion rate of waste concrete, and within a certain range, the smaller the particle size is, the higher the conversion rate is when the slurry concentration is higher, and C in cement clinker minerals is higher 3 S and C 2 The higher the S content.
(2) The current density and the reaction temperature influence the mineral composition mainly by influencing the electrolytic conversion rate of the waste concrete, and the higher the current density and the higher the reaction temperature, the higher the conversion rate is in a certain range, and C in the cement clinker mineral is 3 S and C 2 The higher the S content.
(3) Other conditions are the same, the heating temperature is changed within a certain range, and the mineral components of the cement clinker are basically unchanged; the lower the pH of the cement clinker mineral C within a certain range when the heating temperature is the same 3 S、C 2 S、C 3 A、C 4 The increase in the AF ratio suggests that calcium dissolution and reaction can be promoted under acidic conditions.
It should be noted that the above embodiments are only some embodiments of the present invention, and the preparation method of the present invention using other parameters obtained through experimental design schemes such as orthogonal experiments can still produce the waste concrete composite phosphogypsum-based electrochemical synthetic cement of the present invention. As can be seen from the summary of the performances of the embodiments of the invention, the strength grade of the waste concrete composite phosphogypsum-based electrochemical synthetic cement is 32.5, the main component is calcium silicate, the initial setting time is 45-70min, the final setting time is less than 17 hours, the flexural strengths of 3 days and 28 days are respectively 3.5-7.5MPa and 5.5-9.6MPa, the compressive strengths of 3 days and 28 days are respectively 17-25MPa and 32.5-38MPa, the chloride ion content is less than 0.1%, the alkalinity coefficient is less than 7.2%, the mud content is not more than 2.8%, the magnesium oxide content is less than 4.1%, the loss on ignition is less than 3%, and the performances are good.
In conclusion, the invention can synthesize cement with good performance at normal pressure and lower temperature. Compared with the prior art, the invention has obvious progress.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the invention.
Claims (10)
1. The preparation method of the waste concrete composite phosphogypsum-based electrochemical synthetic cement is characterized by comprising the following steps of:
s1: pretreating the waste concrete to obtain waste concrete with target granularity;
s2: adding water into the waste concrete, and uniformly stirring to obtain waste concrete slurry;
s3: placing the waste concrete slurry into an electrochemical reaction container for electrolysis, and collecting carbon dioxide and electrolysis products generated by the electrolysis;
s4: adding water, waste soil and phosphogypsum into the electrolysis product, uniformly stirring, and regulating pH to be acidic to obtain calcium ion slurry;
s5: heating the calcium ion slurry under the stirring condition, stopping stirring and heating after the calcium ion slurry is completely converted into cement, naturally cooling and curing to obtain cement clinker;
s6: and grinding and packaging the cement clinker to obtain the waste concrete composite phosphogypsum-based electrochemical synthesized cement.
2. The method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement according to claim 1, wherein in step S1, the pretreatment comprises crushing, washing and sieving.
3. The method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement according to claim 1, wherein in step S1, the target particle size is 0.2-1.5mm.
4. The method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement according to claim 1, wherein in step S2, the concentration of the waste concrete slurry is 0.1-3.2mol/L.
5. The method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement according to claim 1, wherein in step S3, the electrolysis is performed at 220V and the current density is 800-2000A/m 3 The reaction temperature is 30-105 ℃ and the reaction time is 30-60min.
6. The method for preparing the waste concrete composite phosphogypsum-based electrochemical synthetic cement according to claim 1, wherein in the step S4, the amount of the electrolysis product is 50-70% by weight, the amount of the waste soil is 20-30% by weight, the amount of the phosphogypsum is 10-25% by weight, and the balance is water.
7. The method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement according to claim 1, wherein in step S4, the pH value of the calcium ion slurry is 4-7.
8. The method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement according to claim 7, wherein in step S4, sulfuric acid is used to adjust pH.
9. The method for preparing waste concrete composite phosphogypsum-based electrochemical synthetic cement according to any one of claims 1-8, characterized in that in step S5, the stirring rate of the stirring condition is 50-80rad/min; when heating, heating is performed under normal pressure, and the heating temperature is 90-250 ℃.
10. The waste concrete composite phosphogypsum-based electrochemical synthetic cement is characterized by being prepared by adopting the preparation method of the waste concrete composite phosphogypsum-based electrochemical synthetic cement in any one of claims 1-9.
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