CN115636652A - Low-carbon high-strength cementing material taking phosphogypsum as main raw material, preparation method and application thereof - Google Patents

Low-carbon high-strength cementing material taking phosphogypsum as main raw material, preparation method and application thereof Download PDF

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CN115636652A
CN115636652A CN202211339703.8A CN202211339703A CN115636652A CN 115636652 A CN115636652 A CN 115636652A CN 202211339703 A CN202211339703 A CN 202211339703A CN 115636652 A CN115636652 A CN 115636652A
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phosphogypsum
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CN115636652B (en
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鲁浈浈
陈健
张晓青
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Chongqing Jiaotong University
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Abstract

The invention discloses a low-carbon high-strength cementing material taking phosphogypsum as a main raw material, which comprises the phosphogypsum, cement, zeolite, metakaolin, water glass, naOH and a water reducing agent in parts by weight; the adopted metakaolin plays a role in inducing ettringite nucleation, cement and phosphogypsum react under the action of an exciting agent to generate a large amount of ettringite close-packed structures, zeolite absorbs water in a prophase gelling system through a porous structure of the zeolite and is kept in the porous structure, and the zeolite provides the required water for the formation of later-stage strength and further hydration reaction in the system. The strength of the cementing material reaches the national standard requirement, the cementing material can replace the existing cement P.C52.5R, the manufacturing cost is lower than that of P.C 52.5R, the large mixing amount utilizes the industrial solid wastes such as phosphogypsum, and the like, the carbon emission is reduced by more than 80 percent, the cementing material can be applied to the fields of civil engineering and constructional engineering such as roads, bridges, and the like, the preparation process is simple, and the phosphogypsum does not need to be calcined and the like to be pretreated in a complex and high-energy consumption form.

Description

Low-carbon high-strength cementing material taking phosphogypsum as main raw material, preparation method and application thereof
Technical Field
The invention relates to the field of building materials, in particular to a low-carbon high-strength cementing material taking phosphogypsum as a main raw material, a preparation method and application thereof.
Background
Phosphogypsum is industrial waste residue discharged in the process of producing phosphoric acid by a wet method, the appearance is usually black grey or grey white, the main components of the phosphogypsum are calcium sulfate and hydration products thereof, wherein CaSO 4 ·2H 2 The ratio of O is large, and impurities such as phosphide, fluoride and organic matters are also contained. In recent years, the annual average emission of the phosphogypsum in China exceeds 7000 million tons, and a large amount of phosphogypsum is stockpiled due to insufficient comprehensive resource utilization. A large amount of phosphogypsum not only occupies land resources, but also seriously threatens the safety of a water environment by water-soluble phosphorus pentoxide and water-soluble fluorine contained in the phosphogypsum, has larger potential safety hazard of ecological environment, needs to widen the utilization path of the phosphogypsum, and continues to promote the utilization of the phosphogypsum in the fields of novel building materials and the like. A series of defects of the phosphogypsum include organic impurities of phosphorus and fluorine, poor gelling property, low strength, poor water resistance, insufficient early strength and the like, which can generate adverse effects on the strength, the water resistance and other properties of the phosphogypsum-based cementing material, and thus the application of the phosphogypsum-based cementing material is restricted to a certain extent. The existing phosphogypsum solid waste utilization method has the limit of large-scale application because the added value is not high, the doping amount is limited, or toxic substances are not solidified. Generally used as a cement retarder or a concrete admixture, and the strength of the cement retarder or the concrete admixture does not meet the national standard requirement of high-grade cement.
The prior art discloses a high-doping-amount phosphogypsum cement clinker cementing material (CN 111362601A) and a preparation method thereof, wherein the formula of the high-doping-amount phosphogypsum is that 52wt% of phosphogypsum, 23% of cement, 8% of phosphorus slag micro-powder, 17% of fly ash and 1.5% of powder phosphorus system excitant are mixed and ground, 0.6% of water agent phosphorus system excitant is doped to prepare the high-doping-amount phosphogypsum-based cementing material, and the compressive strength can reach 39.68MPa to reach the standard of 32.5 cement after 28 days of curing. Yangwen (CN 111792902A) discloses a high-strength water-resistant phosphogypsum composite cementing material and a preparation method thereof, wherein the phosphogypsum is beta-type phosphogypsum and can be obtained only by high-temperature pretreatment, and various organic waterproofing agents are added, so that the compression strength of the phosphogypsum reaches up to 45MPa, and the national standard requirement of 42.5 cement is met. Tanchong wave (CN 114933427A) discloses a preparation method of all-industrial solid waste based low-carbon cement, wherein the doping amount of solid waste phosphogypsum is only 2-5wt%, and high-temperature treatment is required. Sun Zhengping (CN 106747186A) discloses ardealite-based water for curingThe concrete curb prepared from the cementitious composite and the preparation method thereof comprise the components of blast furnace slag as a main component with a proportion of over fifty percent, metakaolin as a component with low metakaolin content, only water glass as an alkali activator, and the mechanical strength of the metakaolin mainly depends on the volcanic ash effect of the slag, and limestone, metakaolin and CaF as the components 2 Is mainly used for adjusting coagulation and does not participate in the formation of mechanical strength. Wanxinlong in literature (application of phosphogypsum in slag-metakaolin geopolymer) applies phosphogypsum in slag-metakaolin geopolymer, the highest doping amount is 30wt%, and phosphogypsum in the system needs high-temperature pretreatment. In the literature (An eco-friendly phosphorus-based complementary materials, performance optimization and enhancement mechanisms), phosphogypsum is applied to slag-cement-metakaolin, the highest doping amount is 45%, the strength of the system is mainly formed by the reaction of slag and phosphogypsum, the material can be realized only by adjusting the ph to 11.8 through a wet grinding process, and the 3-day strength of the system is only about 11Mpa and does not reach the national standard of cement application. In another document (Recycling of phosphorus in eco-excess-phase center: synergistic effects of metaolin and slag additives on moisture, strength and microstructure) it is mentioned that slag and metakaolin act in a system with a strength-forming mechanism that the slag and phosphogypsum form ettringite under the action of metakaolin, and cement acts in a system with a function of adjusting the pH value due to a smaller amount of cement added. In view of published patent conditions, the related patent technologies at present mainly relate to the preparation of gelled materials or low-carbon cement by pretreating industrial waste residues such as phosphogypsum, slag, fly ash, metakaolin and the like.
Disclosure of Invention
In view of the above, the invention aims to provide a low-carbon high-strength cementing material taking phosphogypsum as a main raw material, a preparation method and an application thereof, and solves the problems of poor working performance and mechanical property and the like of the existing phosphogypsum-based cementing material.
The low-carbon high-strength cementing material with phosphogypsum as the main raw material comprises, by weight, 30-70 parts of phosphogypsum, 15-35 parts of cement, 5-10 parts of zeolite, 10-30 parts of metakaolin, 0.1-0.4 part of water glass, 0.6-0.8 part of NaOH and 0.4-0.8 part of a water reducing agent;
further, the raw materials comprise 50 parts of phosphogypsum, 25 parts of cement, 7 parts of zeolite, 20 parts of metakaolin, 0.3 part of water glass, 0.7 part of NaOH and 0.6 part of water reducing agent in parts by weight;
further, the water reducing agent is a melamine water reducing agent;
furthermore, the phosphogypsum is one or more of raw phosphogypsum, semi-hydrated phosphogypsum, natural gypsum and desulfurized gypsum with gelling property;
further, the particle size of the zeolite is 200 mesh.
The invention also discloses a preparation method of the low-carbon high-strength cementing material taking the phosphogypsum as the main raw material, which comprises the following steps:
a. uniformly mixing phosphogypsum, cement, zeolite and metakaolin to obtain an inorganic powder mixture;
b. and adding water, an alkali activator and a water reducing agent into the inorganic powder mixture, and uniformly stirring to obtain the low-carbon high-strength cementing material.
The invention also discloses application of the low-carbon high-strength cementing material taking the phosphogypsum as a main raw material, and application of the low-carbon high-strength cementing material taking the phosphogypsum as a main raw material in preparing concrete.
The invention has the beneficial effects that: the invention discloses a low-carbon high-strength cementing material taking phosphogypsum as a main raw material, a preparation method and application thereof. The strength of the cementing material reaches the national standard requirement, the cementing material can replace the existing cement P.C 52.5R, the manufacturing cost is lower than that of P.C 52.5R, the large-dosage utilization of industrial solid wastes such as phosphogypsum is realized, the carbon emission is reduced by more than 80%, the cementing material can be applied to the fields of civil engineering and constructional engineering such as roads and bridges, the preparation process is simple, and the phosphogypsum does not need to be calcined and other complex and high-energy consumption form pretreatment.
Drawings
The invention is further described below with reference to the following figures and examples:
FIG. 1 is an SEM photograph of cement curing 3d for example 3;
FIG. 2 is an SEM photograph of cement curing 7d for example 3;
FIG. 3 is an SEM photograph of cement curing 28d prepared in example 3;
FIG. 4 is an XRD pattern of cured cement 3d, 7d,28d prepared in example 3;
FIG. 5 is an IR spectrum of cement curing compositions 3d, 7d, and 28d prepared in example 3.
Detailed Description
The low-carbon high-strength cementing material taking the phosphogypsum as the main raw material comprises, by weight, 30-70 parts of phosphogypsum, 15-35 parts of cement, 5-10 parts of zeolite, 10-30 parts of metakaolin, 0.1-0.4 part of water glass, 0.6-0.8 part of NaOH and 0.4-0.8 part of a water reducing agent;
the cement and the metakaolin have obvious influence on improving the early mechanical strength and the softening coefficient of the phosphogypsum-based cementing material system, and directly participate in the mechanical strength forming process. The zeolite mainly absorbs moisture in the reaction process in the early stage of the reaction, provides the moisture required for the further hydration reaction of the gelled material system in the later stage of the reaction process, improves the later stage strength of the gelled material system to reach 69Mpa at most, and meets the national standard requirement of P.C 52.5R cement in each index. Therefore, in the formula of the invention, metakaolin plays a role of inducing ettringite nucleation, cement and phosphogypsum react under the action of an exciting agent (water glass and sodium hydroxide) to generate a large amount of ettringite close-packed structures, zeolite absorbs water in the early stage reaction through the porous structure of the zeolite and keeps the water in the porous structure, and water required by the cement further hydration reaction is provided for the formation of the later strength in the system.
The single phosphogypsum has the problems of low strength, high water absorption and water expansion, so that a ternary system of cement and metakaolin is adopted for three-phase compounding, a large number of experiments show that the highest compressive strength of the phosphogypsum can reach 51.3MPa after being cured for 28 days, a fourth-phase material zeolite is added, the later-stage mechanical strength of the phosphogypsum is surprisingly and unexpectedly found to be greatly improved, the highest compressive strength of the phosphogypsum can reach 38.3MPa after being cured for 3 days, the flexural strength can reach 5.0MPa, the highest compressive strength of the phosphogypsum can reach 69MPa after 28 days, the flexural strength can reach 8.9MPa, the softening coefficient can reach 0.89, and the requirements of GB175-2020 general Portland cement P.C 52.5R are met.
XRD data analysis shows that in a four-phase cementing material system, under the action of an alkali activator, cement firstly undergoes hydration reaction to generate C-S-H, and SiO generates with the increase of reaction time 2 The characteristic peak is enhanced, which indicates that C-A-S-H is generated and CaSO in phosphogypsum 4 Further reacting to generate ettringite, when curing for 3d, a large amount of ettringite is generated under the induction of metakaolin, then the ettringite crystal grows up along with the increase of the curing time to 7d,28d, and the structure becomes more compact and dense. From the FTIR results it can be seen that its subsequent strength improvement comes from the further perfection of the ettringite crystals.
The beneficial effects of the four-phase cementing material system adopting the phosphogypsum, the cement, the zeolite and the metakaolin are as follows:
(1) Because of the nucleation inducing effect of metakaolin, enough phosphogypsum provides Ca2+ and SO4 required by the reaction 2- A large amount of ettringite structures can be generated in the initial reaction stage, and C-S-H generated by cement hydration enables the cement to have high initial performance, and the 3d compressive strength can reach 38.3MPa.
(2) Due to the existence of the porous zeolite, water can be absorbed in the early stage to provide water for further hydration reaction in the later stage and structural improvement, so that the later-stage strength is further improved, and the compressive strength of the zeolite can reach 69MPa after 28-day maintenance.
(3) The phosphogypsum can be doped by up to 50 percent, the carbon emission and the energy consumption in the production process of the common cement are greatly reduced, the mechanical strength index of the system meets the requirement of GB175-2020 Portland Cement for general use, the application range of the system is greatly expanded, and the application value and the utilization rate of the phosphogypsum are improved.
(4) The cementing material is used for preparing concrete test blocks, the compressive strength of the concrete test blocks can reach 80MPa after 28d of maintenance, and the working performance is excellent.
The preferable embodiment is that the raw materials comprise 50 parts of phosphogypsum, 25 parts of cement, 7 parts of zeolite, 20 parts of metakaolin, 0.3 part of water glass, 0.7 part of NaOH and 0.6 part of water reducing agent by weight, and the cement adopts 42.5 or 52.5 parts of ordinary silicate cement
In the embodiment, the water reducing agent is a melamine water reducing agent; the phosphogypsum is one or more of raw phosphogypsum, semi-hydrated phosphogypsum, natural gypsum and desulfurized gypsum with gelling property; micron-sized zeolite with the particle size of 200 meshes is adopted.
The preparation method of the low-carbon high-strength cementing material taking the phosphogypsum as the main raw material comprises the following steps:
a. uniformly mixing phosphogypsum, cement, zeolite and metakaolin to obtain an inorganic powder mixture;
b. adding water, an alkali activator and a water reducing agent into the inorganic powder mixture, and uniformly stirring to obtain a low-carbon high-strength cementing material; the preparation process is simple, and compared with the existing preparation process, the phosphogypsum adopted by the invention does not need complex and high-energy-consumption pretreatment such as calcination and the like.
The cementing material is used for preparing concrete test blocks, the compressive strength of the concrete test blocks can reach 80MPa after 28d of maintenance, and the working performance is excellent.
Example one
The proportions of the raw materials and the properties of the P.C 325 cement (test pieces of cement mortar with 40 mm. Times.40 mm. Times.160 mm prism are prepared in accordance with GB/T17671-2021 "Cement mortar Strength test method" to measure the compressive strength and flexural strength) were determined in the same manner as in the following examples, and in the following examples, the activator is a mixture of water glass and sodium hydroxide.
Figure BDA0003915756410000061
Example two
Figure BDA0003915756410000062
EXAMPLE III
Figure BDA0003915756410000063
Example four
Figure BDA0003915756410000071
EXAMPLE five
The low-carbon high-strength cementing material taking phosphogypsum as a main raw material is used for preparing concrete, and the raw material proportion and the C50 concrete performance are as follows:
Figure BDA0003915756410000072
in the above examples, as shown in FIG. 1, when the cement prepared in example 3 was cured for 3 days, C-S-H, C-A-S-H and ettringite were formed by hydration, and ettringite was randomly overlapped and had large pores.
As shown in FIG. 2, when the cement prepared in example 3 was cured for 7d, the C-A-S-H gel gradually reacted to form ettringite with increasing curing time, and ettringite crystals gradually grown and oriented with decreasing pores.
As shown in FIG. 3, when the cement prepared in example 3 was cured for 28d, the C-S-H and C-A-S-H gels reacted gradually to form ettringite with increasing curing time, and ettringite crystals gradually grown and had se:Sub>A certain directionality and pores gradually decreased.
As shown in FIG. 4, XRD patterns of cured 3d, 7d and 28d of the cementing materials prepared in example 3 and CaSO in the cementing system 4 ·2H 2 O takes part in hydration reaction, caSO 4 ·2H 2 The characteristic peak of O is gradually reduced; increase in the amount of C-S-H and C-A-S-H produced, indicative of SiO 2 Enhancing a characteristic peak; calcium alumThe generation amount of the ettringite is increased, the ettringite crystal gradually grows, and the characteristic peak of the ettringite is enhanced; when the diffraction angle is between 20 and 40 degrees, a section of raised dispersion diffraction peak is formed, and the dispersion diffraction peak is a geopolymer hydration product excited by water glass, namely a silicon-aluminum polymer.
As shown in FIG. 5, the infrared spectrum of the cured cement prepared in example 3 at 3d, 7d,28d was 3541cm -1 、3406cm -1 、1685cm -1 、1621cm -1 、2242cm -1 、2119cm -1 The strength of the peaks is reduced along with the increase of the hydration time, which proves that CaSO4.2H2O further participates in the hydration reaction, and the Al-O-Si asymmetric stretching vibration is formed at the position of 1011cm < -1 > to gradually form the peak, which indicates that the generation amount of the silicon-aluminum polymer is gradually increased.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (7)

1. A low-carbon high-strength cementing material taking phosphogypsum as a main raw material is characterized in that: the raw materials comprise, by weight, 30-70 parts of phosphogypsum, 15-35 parts of cement, 5-10 parts of zeolite, 10-30 parts of metakaolin, 0.1-0.4 part of water glass, 0.6-0.8 part of NaOH and 0.4-0.8 part of water reducing agent.
2. The low-carbon high-strength cementing material taking phosphogypsum as a main raw material according to claim 1, which is characterized in that: the raw materials comprise, by weight, 50 parts of phosphogypsum, 25 parts of cement, 7 parts of zeolite, 20 parts of metakaolin, 0.3 part of water glass, 0.7 part of NaOH and 0.6 part of a water reducing agent.
3. The low-carbon high-strength cementing material taking phosphogypsum as a main raw material according to claim 1, which is characterized in that: the water reducing agent is a melamine water reducing agent.
4. The low-carbon high-strength cementing material taking phosphogypsum as a main raw material according to claim 2, which is characterized in that: the phosphogypsum is one or more of raw phosphogypsum, semi-hydrated phosphogypsum, natural gypsum and desulfurized gypsum with gelling property.
5. The low-carbon high-strength cementing material taking phosphogypsum as the main raw material according to claim 3, which is characterized in that: the particle size of the zeolite is 200 meshes.
6. The preparation method of the low-carbon high-strength cementing material taking the phosphogypsum as the main raw material according to claim 1 is characterized by comprising the following steps:
a. uniformly mixing phosphogypsum, cement, zeolite and metakaolin to obtain an inorganic powder mixture;
b. and adding water, an alkali activator and a water reducing agent into the inorganic powder mixture, and uniformly stirring to obtain the low-carbon high-strength cementing material.
7. The application of the low-carbon high-strength cementing material taking the phosphogypsum as the main raw material is characterized in that: the application of the low-carbon high-strength cementing material taking the phosphogypsum as the main raw material in preparing the concrete.
CN202211339703.8A 2022-10-28 2022-10-28 Low-carbon high-strength cementing material with phosphogypsum as main raw material, preparation method and application thereof Active CN115636652B (en)

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