CN117816718B - A method and structure for storing CO2 in solid waste polymer - Google Patents
A method and structure for storing CO2 in solid waste polymerInfo
- Publication number
- CN117816718B CN117816718B CN202410029773.6A CN202410029773A CN117816718B CN 117816718 B CN117816718 B CN 117816718B CN 202410029773 A CN202410029773 A CN 202410029773A CN 117816718 B CN117816718 B CN 117816718B
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- geopolymer
- solid waste
- industrial solid
- injection pipe
- sealing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/55—Slag
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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
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明属于工业固废资源化利用和CO2封存技术领域，涉及一种固废基地聚物封存CO2的方法及结构。该方法首先将地聚物A经浇筑、养护制得预制板；再将预制板拼接成立体预制件，在立体预制件的一侧贯穿接入注入管，并在预制件外除注入管口以外的区域涂覆地聚物A，完全终凝，形成地聚物密闭层，得到封存CO2的隔离箱；然后通过注入口向封存CO2的隔离箱内泵入地聚物B和液态CO2，结束后封堵注入管口；最后在封存CO2的隔离箱外涂抹硅溶胶，封堵气孔，完成CO2封存。该方法不仅可以进行CO2物理和化学同步封存，还实现了固废的资源化利用，从而降低固废堆放对土地和环境的污染以及CO2排放引起的温室效应问题。
The present invention belongs to the technical field of resource utilization of industrial solid waste and CO2 sequestration, and relates to a method and structure for sequestering CO2 using a solid waste-based geopolymer. The method first involves casting and curing geopolymer A to produce a prefabricated board; then, the prefabricated boards are assembled into a three-dimensional prefabricated component, an injection pipe is inserted through one side of the three-dimensional prefabricated component, and geopolymer A is coated on the outside of the prefabricated component except for the injection pipe port. The geopolymer is completely final-set to form a geopolymer sealing layer, thereby obtaining an isolation box for sealing CO2 ; then, geopolymer B and liquid CO2 are pumped into the isolation box for sealing CO2 through the injection port, and the injection pipe port is sealed after completion; finally, silica sol is applied to the outside of the isolation box for sealing CO2 to seal the pores, thereby completing the CO2 sequestration. This method not only allows for simultaneous physical and chemical sequestration of CO2 , but also realizes the resource utilization of solid waste, thereby reducing the pollution of land and the environment caused by solid waste stacking and the greenhouse effect caused by CO2 emissions.
Description
Technical Field
The invention belongs to the technical field of industrial solid waste resource utilization and CO 2 sealing and storing, and relates to a method and a structure for sealing and storing CO 2 by solid waste base polymers.
Background
Global warming has become a widely focused and urgent issue in international society at present, and carbon sequestration technology has a strong potential in reducing carbon dioxide emissions in energy systems, solid waste mineralization chemical sequestration including CO 2 and direct geological physical sequestration of CO 2. The mineralization and the sealing of the solid waste of CO 2 are realized by carrying out acid-base neutralization reaction on the solid waste rich in Ca, mg and the like and CO 2 to generate stable inorganic carbonate, thereby achieving the purposes of capturing and sealing CO 2 for a long time. However, the method has higher requirements on the types of solid wastes, the solid wastes must contain more active alkaline metals, and the solid wastes can be sealed according to the stoichiometric ratio, so that the sealing quantity is limited. The geological sequestration of CO 2 refers to the sequestration by directly injecting CO 2 into a deep saline water layer, depleted hydrocarbon reservoirs and other geological structures within the depth range of 800-3500 meters below the ground. More than 90% of the total potential of geological storage is in a deep saline water layer, and only a few areas in land have sealing conditions and have no wide applicability.
Along with the development of industry, solid waste piles have a large amount of impurities and harmful substances, the treatment difficulty is high, and the piling up of the solid waste piles brings great pressure to resources and environment.
At present, research has shown that steel slag has inherent alkalinity, and calcium oxide (CaO) and magnesium oxide (MgO) have higher reactivity after being dissolved in aqueous solution, thus being more suitable for mineral carbonation. The mineralization and fixation of CO 2 by steel slag can transfer unstable components (such as free CaO and MgO possibly cause the expansion and cracking of concrete, and the dissolution of heavy metals such as vanadium and chromium possibly pollute soil and groundwater) into carbonate, so that the emission of CO 2 can be reduced, and the stability problem of steel slag concrete can be solved. Fly ash is a basic industrial solid waste, and the yield is rich despite the relatively low content of free CaO, and the circulating fluidized bed fly ash generally has higher CO 2 sealing capability because the desulfurization efficiency of the fly ash is 30-45 percent and the fly ash contains 20-30 percent of CaO.
The Chinese patent application CN116060414A discloses a method for sealing and utilizing slurry solid waste reinforced carbon dioxide, which adopts solid waste materials mainly comprising fly ash and solid carbon materials mainly comprising steel slag, and injects high-flow, low-viscosity and delayed solid waste slurry into an oil reservoir to assist carbon dioxide displacement, so that compared with the traditional backfilled oil-based drilling waste, the method has the advantages that the consumed solid waste is various in selection, and a large amount of industrial solid waste can be consumed, and the multiple utilization of the solid waste is realized.
However, the research of the current solid waste mineralization sealing is mainly focused on steel slag, fly ash and the like, but the current industrial solid waste has the problems of large discharge amount, multiple types and the like, so that in order to fully realize the recycling of resources, the deep research on the application of various industrial solid wastes to CO 2 sealing is necessary. In addition, the physical parameters such as reservoir density, resistivity, seismic wave speed and the like are changed by injecting CO 2 during physical geological storage, and physical preconditions are provided for safety monitoring by using geophysical methods such as earthquake, electromagnetism and the like. Therefore, the synergistic effect of physical geological storage and chemical mineralization storage of solid wastes is expected to become the most feasible technical route for solving the problems of solid waste storage and carbon emission reduction.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method and a structure for sealing and storing CO 2 by using solid waste base polymers, which can realize the reduction of waste, the recycling and the safe disposal and realize the emission reduction of CO 2.
The technical scheme of the invention is as follows:
A method for sequestering CO 2 by solid waste base polymers, comprising the steps of:
(1) Preparing a precast slab, namely pouring and curing the geopolymer A to obtain the precast slab;
(2) Preparing an isolation box for sealing CO 2, namely splicing the prefabricated plate prepared in the step (1) into a solid prefabricated member, penetrating and connecting an injection pipe at one side of the solid prefabricated member, coating a geopolymer A outside the prefabricated member except an injection pipe orifice, and completely final solidifying to form a geopolymer sealing layer;
(3) Pumping geopolymer B and liquid CO 2 into an isolation box for sealing CO 2 through an injection pipe, and sealing the orifice of the injection pipe after the process is finished;
(4) And (3) a plugging process, namely coating silica sol outside the isolation box for plugging CO 2, plugging air holes, and completing CO 2 plugging.
Further, the geopolymer A is prepared from at least one industrial solid waste including carbide slag, steel slag and coal-fired solid sulfur ash (CFB ash), the geopolymer B is prepared from the industrial solid waste including carbide slag, and the carbide slag content in the geopolymer B is higher than that of the geopolymer A.
Still further, the geopolymer A is prepared from at least one industrial solid waste including desulfurized gypsum, fly ash, silicomanganese slag and coal gangue, and the geopolymer B is prepared from at least one industrial solid waste including slag, steel slag and coal-fired solid sulfur ash (CFB ash).
Further, the geopolymer B is prepared from at least one industrial solid waste including desulfurized gypsum, fly ash, silicomanganese slag and coal gangue.
The industrial solid waste carbide slag contains more calcium ions and can be used as an alkaline excitant, the steel slag and slag contain active minerals such as tricalcium silicate (CA 3SiO5), dicalcium silicate (CA 2SiO4), ferro-aluminate and the like with hydraulic gelation property, the coal-fired solid sulfur ash (CFB ash) contains fly ash and calcium sulfate, and calcium oxide (or carbide slag) which does not completely react, and the industrial solid waste carbide slag also has higher activity and can generate higher early strength, and in addition, the industrial solid waste carbide slag is further matched with silicon-aluminum elements in solid wastes such as fly ash, coal gangue and the like, thereby generating the amorphous colloid of the cadherite and C-A-S-H and generating higher strength.
Therefore, in order to achieve a better CO 2 sealing effect without leakage, the invention provides higher early strength for the geopolymer A through the selection of the types of industrial solid wastes, and secondly, when the CO 2 injected into the isolation box contacts with the geopolymer A precast slab, the CO 2 can further react with alkaline calcium and magnesium ions in the interior to generate calcium carbonate to generate volume expansion, so that pores are further sealed, and the leakage of CO 2 is avoided by multi-layer insurance.
Preferably, the geopolymer A and the geopolymer B are prepared from at least three industrial solid wastes, and three solid waste components, particularly when at least one of carbide slag, steel slag and coal-fired solid sulfur ash (CFB ash) is contained in the three solid wastes, the solid wastes can form ettringite which can provide early strength and C-A-S-H amorphous colloid with long-term strength through coupling reaction, and the forward gain is generated on the mechanical properties of the geopolymer.
More preferably, the amount of any industrial solid waste is 10-50% of the total amount of the industrial solid waste, and when a certain component is too much, other components are too little to provide components and elements required by reaction balance, the mechanical properties of the finally formed geopolymer are seriously affected, and the plugging effect (sealing property) is influenced to a certain extent.
When the industrial solid wastes used in the preparation process of the local polymer A are at least three:
alternatively, the industrial solid waste is any one of carbide slag, steel slag and coal-fired solid sulfur ash (CFB ash), and at least two of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue, or any two of carbide slag, steel slag and coal-fired solid sulfur ash (CFB ash), and at least one of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue, or at least three of carbide slag, steel slag and coal-fired solid sulfur ash (CFB ash), and at least one of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue.
When the industrial solid wastes used in the preparation process of the local polymer B are at least three:
Optionally, the industrial solid waste is at least two of carbide slag and desulfurized gypsum, fly ash, silicomanganese slag and coal gangue, or at least two of carbide slag and slag, steel slag and coal-fired solid sulfur ash (CFB ash), or at least one of carbide slag and slag, steel slag and coal-fired solid sulfur ash (CFB ash) and at least one of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue.
Further, the water-cement ratio of the geopolymer A is 0.3-0.7.
Further, the water-cement ratio of the geopolymer B is 0.4-0.7.
The lower the water-cement ratio is, the higher the strength of the polymer is, the higher the plugging effect is realized by reasonably limiting the water-cement ratio of the geopolymer A, and the geopolymer B does not need to generate strength but needs more alkaline substances to mineralize carbon dioxide, so more water can be added to help mineralization, the water-cement ratio is properly increased, but not too much, more space of industrial solid wastes and CO 2 can be occupied, the total amount of CO 2 filled is reduced, and the CO 2 plugging efficiency is reduced.
Further, the volume ratio of the geopolymer B to the liquid CO 2 is 1:0.2-0.4, and the geopolymer B contains more alkaline elements through the control of the volume ratio of the geopolymer B to the liquid CO 2, so that the geopolymer B can be hopefully mineralized with CO2 for a long time to generate carbonate substances, thereby realizing better chemical sealing and thoroughly avoiding the risk of CO2 overflow. The geopolymer B and liquid CO 2 may fill the interior space of the insulation can where CO 2 is sequestered.
Further, in the step (1), the curing temperature is 25-100 ℃, the curing humidity is 80-95%, and the curing time is 4-24 hours.
Further, in the step (4), the silica sol is any one of acidity, neutrality and alkalinity, and the silica content in the silica sol is more than 30%.
In some embodiments of the invention, the preparation method of the geopolymer specifically comprises the steps of mixing industrial solid wastes according to a certain proportion, ball milling for 15-120min, and adding water for mixing.
Further, the particle size of the industrial solid waste is <100 μm.
The invention also provides a structure for implementing the method for sequestering CO 2 by the solid waste base polymer.
The structure is an isolation box for sealing CO 2, which is composed of a three-dimensional prefabricated member, an injection pipe and a geopolymer sealing layer coated on the outer layer of the three-dimensional prefabricated member except for an injection pipe orifice, wherein the outer layer of the isolation box is coated with a silica gel layer, the three-dimensional prefabricated member is formed by splicing prefabricated plates, and the injection pipe penetrates through any side of the three-dimensional prefabricated member.
Further, the thickness of the geopolymer sealing layer is 3-8cm, and the side length or length and width can be adjusted according to actual requirements. The geopolymer sealing layer can combine the three-dimensional prefabricated members to form a complete sealing wall and form an internal reserved space.
Further, the thickness of the silica sol layer is 0.1-1cm. The silica gel layer can further seal the air holes and avoid CO 2 from extravasation.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention discloses an isolation box for preparing and sealing CO 2 by using polymer prepared from solid waste, which can solve the problem of large-scale absorption of the solid waste, change industrial solid waste into valuable, and realize the resource utilization of the solid waste.
(2) The invention further screens the industrial solid waste types and the proportion of the amounts of the components, and controls the proportion of the geopolymer B and the liquid CO 2, so that better chemical sealing effect of CO 2 can be realized.
(3) The invention can realize the physical and chemical synchronous sealing of CO 2, has large sealing quantity, strong applicability, low sealing cost, better economy and practicability and can be popularized and used on a large scale.
(4) The B geopolymer with more carbide slag content and liquid CO 2 are synchronously injected, the generated calcium carbonate micro-nano particles can seal pores of the geopolymer A, and the sol smeared on the outermost layer of the cube prefabricated member can further seal the pores, prevent CO 2 from seeping, and further ensure that the geopolymer isolation box sealed with CO 2 is safely disposed for a long time in places such as mines, pits, deep sea and the like.
Drawings
FIG. 1 is a schematic diagram of the structure of the solid waste base polymer sequestering CO 2 of the present invention.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. The following is merely exemplary of the scope of the invention as claimed and many variations and modifications of the invention will be apparent to those skilled in the art in light of the disclosure, which are intended to be within the scope of the invention as claimed.
(1) Preparing a prefabricated plate:
the geopolymer A is subjected to casting molding, curing and reinforcing to prepare the prefabricated plate with certain thickness and size (the prefabricated plate is shown in figure 1).
In the curing and reinforcing process, the curing temperature is 25-100 ℃, the curing humidity is 80-95%, and the curing time is 4-24 hours.
In the invention, the preparation method of the geopolymer A comprises the following steps:
s1, mixing one or more industrial solid wastes;
s2, ball milling industrial solid waste or mixed industrial solid waste for 15-60min to obtain solid waste particles with the particle size smaller than 100 mu m;
And S3, adding water into the solid waste particles, and uniformly mixing to obtain the geopolymer A.
In the present invention, the industrial solid waste includes at least one of carbide slag, steel slag, and coal-fired solid sulfur ash (CFB ash).
Preferably, the industrial solid waste further comprises at least one of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue.
Further preferably, the industrial solid waste is at least three.
When the industrial solid waste is at least three, the industrial solid waste is optionally any one of carbide slag, steel slag and coal-fired solid sulfur ash (CFB ash), and at least two of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue, or any two of carbide slag, steel slag and coal-fired solid sulfur ash (CFB ash), and at least one of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue, or at least three of carbide slag, steel slag and coal-fired solid sulfur ash (CFB ash), and at least one of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue.
In the present invention, the water-cement ratio of the geopolymer A is 0.3 to 0.7.
(2) Preparing an isolation box for sealing CO 2:
Splicing the prefabricated plates prepared in the step (1) into a solid prefabricated member, penetrating one side of the solid prefabricated member and accessing an injection pipe (the injection pipe is shown in figure 1), coating a geopolymer A with a certain thickness outside the prefabricated member except the outside area of the injection pipe orifice, completely final solidifying to form a geopolymer sealing layer (the geopolymer sealing layer is shown in figure 1), and forming an internal reserved space for injecting liquid CO 2, so that physical sealing of CO 2 can be realized.
In the invention, when the isolation box for sealing CO 2 is prepared, the industrial solid waste or water cement ratio used for preparing the geopolymer A coated in the outer area of the three-dimensional prefabricated part can be the same as that of the geopolymer A used for preparing the prefabricated plate in the step (1).
(3) The injection process comprises the following steps:
And pumping the geopolymer B and the liquid CO 2 into the inner space of the isolation box for storing the CO 2 through the injection opening, sealing the injection opening after the end, namely pushing the prefabricated plate A with the same size and hole into the injection opening, covering the geopolymer A, and carrying out local heating maintenance for 1 hour.
In the present invention, the geopolymer B is prepared by the method of the same as the geopolymer A.
In the invention, the industrial solid waste used in the preparation process of the geopolymer B comprises carbide slag.
In the present invention, the industrial solid waste used in the preparation process of the geopolymer B further comprises at least one of slag, steel slag, and coal-fired solid sulfur ash (CFB ash).
In the invention, the industrial solid waste used in the preparation process of the geopolymer B also comprises at least one of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue.
Preferably, the industrial solid wastes used in the preparation process of the geopolymer B are at least three.
When the industrial solid waste is at least three, optionally, the industrial solid waste is at least two of carbide slag and desulfurized gypsum, fly ash, silicomanganese slag and coal gangue, or at least two of carbide slag and slag, steel slag and coal-fired solid sulfur ash (CFB ash), or at least one of carbide slag and slag, steel slag and coal-fired solid sulfur ash (CFB ash) and at least one of desulfurized gypsum, fly ash, silicomanganese slag and coal gangue.
In the present invention, when the industrial solid wastes used in the preparation process of the geopolymer a and the geopolymer B each include carbide slag, it is preferable that the content of carbide slag in the industrial solid waste used in the preparation process of the geopolymer B is higher than that in the industrial solid waste used in the preparation process of the geopolymer a.
In the present invention, the water-cement ratio of the geopolymer B is 0.4 to 0.7.
According to the invention, chemical sequestration of CO 2 can be realized by synchronous injection of the geopolymer B and the liquid CO 2.
Further, the volume ratio of the geopolymer B to the liquid CO 2 is 1:0.2-0.4, and the geopolymer B contains more alkaline elements through the control of the volume ratio of the geopolymer B to the liquid CO 2, so that the geopolymer B can be hopefully mineralized with CO2 for a long time to generate carbonate substances, thereby realizing better chemical sealing and thoroughly avoiding the risk of CO2 overflow.
(4) The plugging process comprises the following steps:
And (3) coating silica sol (silica sol layer is shown in figure 1) outside the isolation box for sealing CO 2, and sealing the air holes to finish CO 2 sealing. By further plugging the silica sol, CO 2 extravasation can be effectively avoided, and long-term safe disposal of the plugging is further ensured.
In the invention, the silica sol is one of acidity, neutrality and alkalinity, and the silica content in the silica sol is more than 30%.
As described above, the invention also provides a structure (see FIG. 1) for implementing the method, which is an isolation box for storing CO 2, wherein the isolation box comprises a three-dimensional prefabricated member, an injection pipe and a geopolymer airtight layer coated on the outer layer of the three-dimensional prefabricated member except for the injection pipe opening, the outer layer of the isolation box is coated with a silica gel layer, the three-dimensional prefabricated member is formed by splicing prefabricated plates, and the injection pipe penetrates through any side of the three-dimensional prefabricated member.
In the invention, the thickness of the geopolymer sealing layer is 3-8cm, the side length or length and width can be adjusted according to actual requirements, and the thickness of the silica gel layer is 0.1-1cm.
The CO 2 sealing box obtained according to the scheme has excellent sealing performance and no leakage problem. And the chemical sealing is realized along with the mineralization reaction of the geopolymer B and CO 2, the stock and the pressure of CO 2 in the sealed box are gradually reduced, and the risk of overflowing CO 2 can be thoroughly avoided.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
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| KR920011592A (en) * | 1990-12-19 | 1992-07-24 | 성기영 | Safe disposal and recycling of industrial waste |
| ATE516335T1 (en) * | 2006-08-07 | 2011-07-15 | Prad Res & Dev Nv | GEOPOLYMER COMPOSITION AND ITS APPLICATION FOR CARBON DIOXIDE STORAGE |
| CN115011444A (en) * | 2014-12-18 | 2022-09-06 | 加州理工学院 | Method and apparatus for CO2 storage |
| JP7423482B2 (en) * | 2020-09-04 | 2024-01-29 | 株式会社東芝 | Solid waste treatment method and solid waste treatment equipment |
| CN114314588B (en) * | 2021-12-17 | 2023-09-12 | 安徽华塑股份有限公司 | CO in waste gas of lime kiln for producing lime 2 Sealing and recycling method |
| CN115628106B (en) * | 2022-10-18 | 2023-05-19 | 中国矿业大学 | Mine solid waste fluidization filling treatment synergistic carbon dioxide sealing method |
| CN115925381B (en) * | 2022-11-28 | 2024-06-25 | 中国矿业大学 | Calcium-based solid waste light composite slurry for disaster reduction and carbon dioxide sequestration of coal mine and preparation and use methods thereof |
| CN116357392B (en) * | 2023-04-28 | 2025-12-23 | 太原理工大学 | Carbon storage space filling reconstruction-CO in abandoned roadway2Sealing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946255A (en) * | 2017-04-26 | 2017-07-14 | 清华大学 | A kind of near coal-mine coal-burning power plant's waste processing and the method for carbon dioxide sequestration |
| CN109989430A (en) * | 2019-04-17 | 2019-07-09 | 内蒙古科技大学 | A new type of solid waste-based environmentally friendly and durable anti-seepage and anti-seepage structure and anti-seepage barrier material |
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