CN109836115B - Preparation method of grouting filling material - Google Patents
Preparation method of grouting filling material Download PDFInfo
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- CN109836115B CN109836115B CN201910261356.3A CN201910261356A CN109836115B CN 109836115 B CN109836115 B CN 109836115B CN 201910261356 A CN201910261356 A CN 201910261356A CN 109836115 B CN109836115 B CN 109836115B
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
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- 238000009621 Solvay process Methods 0.000 claims description 4
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 235000011941 Tilia x europaea Nutrition 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a preparation method of a grouting filling material, which comprises the following steps: and (3) carrying out wet mixing on the alkaline residue, the fly ash, the bauxite flotation residue and the additive, then carrying out aging treatment, and carrying out solid-liquid separation to obtain the grouting filling material. The method of the invention uses two waste residues of alkaline residue and fly ash of an ammonia process alkali manufacturing plant as raw materials, uses bauxite flotation residue as an auxiliary material, and uses an additive as an auxiliary material to simply and rapidly prepare the grouting filling material, thereby not only realizing the utilization of solid waste, solving the problems of waste accumulation and dust pollution, reducing the manufacturing cost, but also having short coagulation time and high strength which can reach more than 1.2MPa, and realizing the comprehensive utilization of the waste of the alkali manufacturing plant and the emission of bauxite flotation enterprises.
Description
Technical Field
The invention belongs to the technical field of solid waste utilization, and relates to a preparation method of a grouting filling material.
Background
The caustic sludge and the fly ash are two main solid wastes generated by an alkali factory, and the amount of waste liquid and waste residue discharged per 1 ton of alkali produced in the process of producing the soda ash by the ammonia-soda process is about 9-11 m3The solid content is about 300-600 kg, and a large amount of waste residue liquid is accumulated all the year round, thereby occupying a large amount of land and polluting the environment. The water content of the waste caustic sludge is large, and the solid phase specific surface of the slag body is large, so that great difficulty is brought to the comprehensive utilization of the waste caustic sludge. In order to make better use of the solid waste, the main components of the solid waste need to be known to improve the utilization rate.
The main components of the caustic sludge are lime milk for producing soda by an ammonia-soda process and calcium carbonate formed with carbon dioxide, and salt water contained in calcium carbonate fine particle deposits in a calcium oxide, lime milk and flaky aragonite structure state is difficult to naturally seep out and cannot be naturally dried after being stacked in a caustic sludge pool for a long time; the fly ash is commonly called as 'artificial volcanic ash', the main components of the fly ash are silicon oxide and aluminum oxide, and the fly ash is common solid waste generated by a power plant and has large accumulation amount. The bauxite flotation slag is waste residue obtained by grinding bauxite raw ore and then performing a flotation process, and contains various clay ore components such as kaolinite, montmorillonite, illite, pyrophyllite and the like, and a small amount of iron oxide, silicon dioxide, titanium dioxide and the like. At present, a great deal of research work is carried out on the comprehensive treatment of solid wastes such as alkaline residue, fly ash, bauxite flotation slag and the like, for example, the alkaline residue is used as a roadbed material, backfill soil, baking-free brick production and the like. CN 1050173A discloses an alkali residue and fly ash baking-free brick, the raw materials of the baking-free brick comprise alkali residue, fly ash and a composite excitant, and simultaneously, steel slag, an early strength agent and aggregate can also be added, the components are complex, the required cost is high, and the utilization amount of waste is small. CN 104402393A discloses a preparation method of backfill for basic engineering of capital construction, wherein the backfill takes caustic sludge, phosphorus slag and fly ash as raw materials, and is mixed by a wet method to obtain a backfill finished product with a certain water content, but the proportion of the raw materials in the method is not enough to fully utilize the caustic sludge on a large scale.
The grouting filling material is an important building material, the using amount is large, most grouting filling materials contain cement, the cost of the cement is high, and a large amount of CO is generated in the production process2The exhaust gas is discharged, so the development of waste-based grouting filling materials is one of the current research focuses. CN 106278070A discloses a novel grouting filling material, which is prepared from the following raw materials in parts by weight: 5-95 parts of slag, 0-95 parts of red mud and 0-95 parts of carbide slag, and the utilization rate of solid waste residues is high, however, the raw materials are mainly waste materials with similar cement components and different sources, and the transportation cost of the waste materials is high.
In conclusion, how to utilize the waste materials of the alkali factory in a large scale nearby to replace cement to prepare the grouting filling material is one of the practical problems to be solved at present.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a preparation method of a grouting filling material, which takes two alkali factory waste residues of alkali slag and coal ash as raw materials, bauxite flotation slag as an auxiliary material and an additive as an auxiliary material, so that the grouting filling material is simply and quickly prepared, solid waste is utilized, the manufacturing cost is reduced, the obtained material has short coagulation time and high strength, the purpose of grouting can be achieved, and a new technical route and a new method are provided for realizing comprehensive utilization of alkali factory waste on a large scale.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a grouting filling material, which comprises the following steps: and (3) carrying out wet mixing on the alkaline residue, the fly ash, the bauxite flotation residue and the additive, then carrying out aging treatment, and carrying out solid-liquid separation to obtain the grouting filling material.
In the invention, the caustic sludge and the fly ash generated in the production process of the alkali factory are used as raw materials, and are mixed with auxiliary materials and additives together by a wet method to enhance the cohesiveness among different raw materials, and the grouting filling material with higher strength is prepared by aging treatment, so that the utilization of solid wastes is realized, and the problems of large occupied area and serious pollution of the wastes of the alkali factory can be effectively solved; the obtained grouting filling material is used as a building material to replace cement with higher cost, and has the advantages of short setting time, high strength, low manufacturing cost and environmental protection.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
As a preferable technical scheme of the invention, the caustic sludge is derived from waste slag discharged in the process of producing soda ash by an ammonia-soda process, and the water content of the caustic sludge is about 50 wt%.
Preferably, the fly ash is from an ammonia soda plant and/or a power plant.
Preferably, the bauxite flotation slag is derived from flotation slag discharged from a bauxite flotation process.
In the invention, the alkaline residue, the fly ash and the bauxite flotation residue can be dry materials or wet materials, when the dry materials are adopted, the raw materials need to be crushed and scattered by water spraying, and the mixing refers to the operation of adding water for loosening or recycling liquid after solid-liquid separation.
In a preferred embodiment of the present invention, the additive includes an inorganic additive and/or an organic polymer additive.
Preferably, the inorganic additive comprises a silicate, preferably sodium silicate.
Preferably, the organic polymer additive includes polyacrylamide.
In the invention, when the silicate is selected as the additive, the aqueous solution of the silicate has stronger cohesiveness, and can play a role in binding and activating mineral particles in the aging process, and the grouting filling material formed by mixing and interaction of the raw material components has high strength, quick hardening, acid and alkali corrosion resistance and good grouting filling performance.
As a preferred technical scheme of the invention, when the alkaline residue, the fly ash, the bauxite flotation residue and the additive are mixed, the dry basis weight parts are respectively as follows: 25 to 70 parts of caustic sludge, for example, 25 parts, 30 parts, 40 parts, 50 parts, 60 parts or 70 parts, but not limited to the recited values, and other values not recited in the above range are also applicable; 20 to 50 parts of fly ash, for example, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts, but not limited to the recited values, and other values not recited in the range of the values are also applicable; bauxite flotation slag 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc., but is not limited to the recited values, and other values not recited in this range of values are equally applicable; the additive is 3 to 20 parts, for example, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 20 parts, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
In the invention, the alkaline residue and the fly ash are used as two main raw materials, the weight proportion of the alkaline residue and the fly ash has influence on the performance of the grouting filling material, if the proportion of the alkaline residue and the fly ash is larger, the dosage of the alkaline residue is too much, and the strength is reduced and the fluidity is large due to the small alkaline residue particles and large water content; if the ratio of the two is too small, i.e. the amount of alkaline residue is too small, the filling between the material particles is not ideal, and fine pores are left, thereby affecting the strength.
Similarly, the use amounts of the auxiliary materials and the additives also affect the properties such as strength of the grouting filling material, and if the use amounts of the auxiliary materials and the additives are less than those of the alkali residue and the fly ash, the mixing uniformity of the slurry is reduced, and the cohesiveness among the raw materials is poor, so that the strength is affected; if the auxiliary materials and the additives are more than the dosage of the alkaline residue and the fly ash, the dosage of the alkaline residue and the fly ash is affected, and the cost is too high.
In a preferred embodiment of the present invention, the solid-liquid weight ratio in the wet mixing is (3 to 8):8, for example, 3:8, 4:8, 5:8, 6:8, 7:8, or 8:8, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the liquid used for wet mixing is an additive solution.
In a preferred embodiment of the present invention, the temperature of the wet mixing is 20 to 40 ℃, for example, 20 ℃, 24 ℃, 27 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃ or 40 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable.
Preferably, the wet mixing is performed under stirring conditions.
Preferably, the stirring rate is 120 to 300r/min, such as 120r/min, 150r/min, 180r/min, 210r/min, 240r/min, 270r/min or 300r/min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
In a preferred embodiment of the present invention, the aging time is 0.5 to 48 hours, for example, 0.5 hour, 1 hour, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, 28 hours, 36 hours, 42 hours or 48 hours, preferably 8 to 18 hours.
In a preferred embodiment of the present invention, the solid-liquid separation is filtration.
Preferably, the solid phase obtained by the solid-liquid separation is a grouting filling material.
Preferably, the water content of the grouting filler is 20 to 40 wt%, such as 20 wt%, 23 wt%, 25 wt%, 27 wt%, 30 wt%, 32 wt%, 35 wt%, 38 wt%, or 40 wt%, and the like, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the liquid phase obtained from the solid-liquid separation is returned for wet mixing.
As a preferred technical solution of the present invention, the method comprises: preparing 25-70 parts of alkaline residue, 20-50 parts of fly ash, 20-50 parts of bauxite flotation residue, 3-20 parts of additive and water into a solution by dry weight, and then carrying out wet mixing under stirring conditions, wherein the weight ratio of solid to liquid of the wet mixing is (3-8): 8, the temperature is 20-40 ℃, then carrying out aging treatment for 0.5-48 h, carrying out solid-liquid separation to obtain a grouting filling material with the water content of 20-40 wt%, and returning the obtained liquid phase for wet mixing.
The invention provides a grouting filling material prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method takes the alkaline residue and the fly ash as raw materials, takes the bauxite flotation residue as an auxiliary material, and is supplemented with an additive to prepare the grouting filling material, wherein the strength of the grouting filling material can reach more than 1.2MPa, the setting time is short, and the performance is excellent;
(2) the treatment capacity of the caustic sludge and the fly ash is large, and the method is particularly suitable for filling and enhancing the gaps of the foundation of the underground infrastructure construction site, thereby not only solving the requirement of infrastructure foundation engineering and saving a large amount of resources, but also solving the problems of waste accumulation, dust pollution and other environmental protection problems;
(3) the method has simple process and lower cost, realizes the high-efficiency recycling of waste resources of alkali plants, and provides new application for the bauxite flotation slag.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific embodiment of the invention provides a preparation method of a grouting filling material, which comprises the following steps: and (3) carrying out wet mixing on the alkaline residue, the fly ash, the bauxite flotation residue and the additive, then carrying out aging treatment, and carrying out solid-liquid separation to obtain the grouting filling material.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of a grouting filling material, which comprises the following steps:
50 parts by weight of alkaline residue, 35 parts by weight of fly ash, 35 parts by weight of bauxite flotation residue, 10 parts by weight of sodium silicate and water are mixed under the stirring condition by a wet method, the solid-liquid weight ratio of the solid raw material to the water is 5:8, the mixing temperature is 30 ℃, then the aging treatment is carried out for 8 hours, the solid-liquid separation is carried out to obtain a grouting filling material with the water content of 30 wt%, and the obtained liquid phase is returned for the wet mixing.
In this embodiment, after the obtained grouting filling material is coagulated, the strength can reach 1.4 MPa.
Example 2:
the embodiment provides a preparation method of a grouting filling material, which comprises the following steps:
and (2) carrying out wet mixing on 70 parts by weight of alkaline residue, 20 parts by weight of fly ash, 25 parts by weight of bauxite flotation residue, 5 parts by weight of sodium silicate and water under the stirring condition, wherein the solid-liquid weight ratio of the solid raw material to the water is 1:1, the mixing temperature is 40 ℃, then carrying out aging treatment for 4 hours, carrying out solid-liquid separation to obtain a grouting filling material with the water content of 20 wt%, and returning the obtained liquid phase to be used for wet mixing.
In this embodiment, after the obtained grouting filling material is coagulated, the strength can reach 1.2 MPa.
Example 3:
the embodiment provides a preparation method of a grouting filling material, which comprises the following steps:
25 parts by weight of alkaline residue, 50 parts by weight of fly ash, 30 parts by weight of bauxite flotation residue, 15 parts by weight of polyacrylamide and water are subjected to wet mixing under the stirring condition, the solid-liquid weight ratio of the solid raw material to the water is 3:8, the mixing temperature is 20 ℃, then the aging treatment is carried out for 16 hours, the solid-liquid separation is carried out to obtain the grouting filling material with the water content of 40 wt%, and the obtained liquid phase is returned for wet mixing.
In this embodiment, after the obtained grouting filling material is coagulated, the strength can reach 1.25 MPa.
Example 4:
the embodiment provides a preparation method of a grouting filling material, which comprises the following steps:
25 parts by weight of alkaline residue, 20 parts by weight of fly ash, 20 parts by weight of bauxite flotation residue, 8 parts by weight of sodium silicate and water are mixed by a wet method under the stirring condition, the solid-liquid weight ratio of the solid raw material to the water is 3:4, the mixing temperature is 35 ℃, then the aging treatment is carried out for 1h, the solid-liquid separation is carried out to obtain the grouting filling material with the water content of 35 wt%, and the obtained liquid phase is returned for wet mixing.
In this embodiment, after the obtained grouting filling material is coagulated, the strength can reach 1.45 MPa.
Example 5:
the embodiment provides a preparation method of a grouting filling material, which comprises the following steps:
and (2) carrying out wet mixing on 70 parts by weight of alkaline residue, 50 parts by weight of fly ash, 50 parts by weight of bauxite flotation residue, 20 parts by weight of sodium silicate and water under the stirring condition, wherein the solid-liquid weight ratio of the solid raw material to the water is 1:2, the mixing temperature is 25 ℃, then carrying out aging treatment for 36 hours, carrying out solid-liquid separation to obtain a grouting filling material with the water content of 25 wt%, and returning the obtained liquid phase to be used for wet mixing.
In this embodiment, after the obtained grouting filler is coagulated, the strength can reach 1.55 MPa.
Example 6:
this example provides a method of making a slip-cast filler material, which is as described with reference to example 2, except that: the using amount of the fly ash is 18 parts by weight, namely the proportion of the alkaline residue to the fly ash is larger.
In this embodiment, the ratio of the caustic sludge to the fly ash is large, so that the ultrafine-particle aqueous caustic sludge generates a rheological phenomenon in a vibration or pressure state, and the strength of the grouting filling material is reduced to about 1.05 MPa.
Example 7:
this example provides a method of making a slip-cast filler material, which is as described with reference to example 3, except that: the using amount of the fly ash is 55 parts by weight, namely the proportion of the alkaline residue to the fly ash is smaller.
In this embodiment, the ratio of the alkaline residue to the fly ash is small, so that the pores of the fly ash powder are not filled with enough ultrafine ammonia alkaline residue, and the strength of the grouting filler material is reduced to about 0.95 MPa.
Example 8:
this example provides a method of making a slip-cast filler material, which is as described with reference to example 4, except that: the amount of sodium silicate used is 22 parts by weight, i.e. the amount of additive used is somewhat greater.
In the embodiment, the use amount of the additive is too large, so that the viscosity of the mixture is too high, the stirring resistance is increased, the mixture is not uniformly mixed, and the strength of the grouting filling material is reduced to about 1.08 MPa.
Example 9:
this example provides a method of making a slip-cast filler material, which is as described with reference to example 5, except that: the amount of sodium silicate used is 2.5 parts by weight, i.e. the amount of additive used is relatively small.
In the embodiment, the use amount of the additive is less, so that the combination effect among the alkaline residue, the fly ash and the bauxite flotation residue is weakened, the setting time of the grouting filling material is long when the grouting filling material is used, and the strength is reduced to 1.02 MPa.
Comparative example 1:
this comparative example provides a method of making a slip-cast filler material, which is as described with reference to example 1, except that: the raw material did not include sodium silicate, i.e. no additive was added.
In the comparative example, as the additive is added during the preparation of the grouting filling material, the alkaline residue, the fly ash and the bauxite flotation residue are simply mixed by a wet method and coagulated after aging treatment, the caking property between the alkaline residue, the fly ash and the bauxite flotation residue is weaker, and the strength is lower and is only about 0.76 MPa.
By integrating the above embodiments and comparative examples, the method of the present invention uses the alkaline residue and the fly ash as main raw materials, uses the bauxite flotation residue as an auxiliary material, and uses the additive as an auxiliary material to prepare the grouting filling material, wherein the strength of the grouting filling material can reach more than 1.2MPa, the setting time is short, and the performance is excellent; the treatment capacity of the alkaline residue and the fly ash is large, so that the basic engineering requirement of capital construction is met, a large amount of resources are saved, the environmental protection problems such as waste accumulation and dust pollution are solved, a new purpose is found for bauxite flotation residue, and the large-scale efficient recycling of waste resources of alkali factories is facilitated.
The applicant states that the process of the present invention is illustrated by the above examples, but the present invention is not limited to the above process, i.e. it is not meant that the present invention must rely on the above process to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials for the invention, additions of additional materials, selection of specific means, etc., are within the scope and disclosure of the invention.
Claims (17)
1. A method of preparing a slip-casting filler material, the method comprising: carrying out wet mixing on alkaline residue, fly ash, bauxite flotation residue and an additive, and then carrying out aging treatment, wherein when the alkaline residue, the fly ash, the bauxite flotation residue and the additive are mixed, the dry basis weight parts are respectively as follows: 25-70 parts of alkaline residues, 20-50 parts of fly ash, 20-50 parts of bauxite flotation residues and 3-20 parts of additives, wherein the additives comprise inorganic additives and/or organic polymer additives, the inorganic additives comprise silicates, the organic polymer additives comprise polyacrylamide, the solid-liquid weight ratio is (3-8): 8 during wet mixing, the grouting filling material is obtained through solid-liquid separation, and the water content of the grouting filling material is 20-40 wt%.
2. The method according to claim 1, characterized in that the caustic sludge is waste residue discharged in the process of producing soda ash by an ammonia-soda process.
3. The method of claim 1, wherein the fly ash is from an ammonia soda plant and/or a power plant.
4. The method of claim 1, wherein the bauxite flotation slag is waste residue from a flotation process of bauxite.
5. The method of claim 1, wherein the inorganic additive is sodium silicate.
6. The method according to claim 1, wherein the caustic sludge, the fly ash, the bauxite flotation slag and the additive are mixed in the following dry basis weight parts: 35-58 parts of alkaline residues; 28-45 parts of fly ash; 25-45 parts of bauxite flotation slag; 12-18 parts of an additive.
7. The method of claim 1, wherein the liquid used for wet mixing is an additive solution.
8. The method according to claim 1, wherein the temperature of the wet mixing is 20 to 40 ℃.
9. The method of claim 1, wherein the wet mixing is performed under agitation conditions.
10. The method according to claim 9, wherein the stirring rate is 120 to 300 r/min.
11. The method according to claim 1, wherein the aging time is 0.5 to 48 hours.
12. The method according to claim 11, wherein the aging time is 8-18 h.
13. The method of claim 1, wherein the solid-liquid separation is filtration.
14. The method according to claim 1, wherein the solid phase obtained by the solid-liquid separation is a grouting packing material.
15. The method according to claim 1, wherein the liquid phase obtained from the solid-liquid separation is returned for wet mixing.
16. The method according to claim 1, characterized in that it comprises: preparing 25-70 parts of alkaline residue, 20-50 parts of fly ash, 20-50 parts of bauxite flotation residue, 3-20 parts of additive and water into a solution by dry weight, and then carrying out wet mixing under stirring conditions, wherein the weight ratio of solid to liquid of the wet mixing is (3-8): 8, the temperature is 20-40 ℃, then carrying out aging treatment for 0.5-48 h, carrying out solid-liquid separation to obtain a grouting filling material with the water content of 20-40 wt%, and returning the obtained liquid phase for wet mixing.
17. A slip-casting filler material obtainable by a method according to any one of claims 1 to 16.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| SU623840A1 (en) * | 1976-11-02 | 1978-09-15 | Алма-Атинский научно-исследовательский и проектный институт строительных материалов | Raw mix for making silical brick |
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| CN1015979B (en) * | 1987-03-14 | 1992-03-25 | 天津市新型建筑材料工业公司研究室 | Production process of building daub soda-residue |
| CN1100485A (en) * | 1993-09-16 | 1995-03-22 | 刘生泰 | Method for making backfill with caustic sludge coal ash |
| CN101412596A (en) * | 2008-10-29 | 2009-04-22 | 中国铝业股份有限公司 | Silicon-aluminum polymeric material and preparation thereof |
| CN104310818B (en) * | 2014-10-15 | 2016-05-25 | 河北工业大学 | A kind of alkaline residue base class cement gel material |
| CN108726926A (en) * | 2017-04-14 | 2018-11-02 | 鄢金松 | A kind of method of red mud and bauxite grown place polymer cement mortar |
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| SU623840A1 (en) * | 1976-11-02 | 1978-09-15 | Алма-Атинский научно-исследовательский и проектный институт строительных материалов | Raw mix for making silical brick |
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