CN111389866A - Method for neutralizing and mineralizing acid tailings - Google Patents
Method for neutralizing and mineralizing acid tailings Download PDFInfo
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- CN111389866A CN111389866A CN202010262226.4A CN202010262226A CN111389866A CN 111389866 A CN111389866 A CN 111389866A CN 202010262226 A CN202010262226 A CN 202010262226A CN 111389866 A CN111389866 A CN 111389866A
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- tailings
- acid
- neutralizing
- mineralized
- modifier
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- 239000002253 acid Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000003472 neutralizing effect Effects 0.000 title claims abstract description 24
- 230000001089 mineralizing effect Effects 0.000 title description 8
- 239000003607 modifier Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000005273 aeration Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 32
- 239000000292 calcium oxide Substances 0.000 claims description 16
- 235000012255 calcium oxide Nutrition 0.000 claims description 16
- 239000005995 Aluminium silicate Substances 0.000 claims description 14
- 235000012211 aluminium silicate Nutrition 0.000 claims description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims 1
- 238000006062 fragmentation reaction Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 5
- 239000000428 dust Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000006213 oxygenation reaction Methods 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 239000002689 soil Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910001653 ettringite Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052960 marcasite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- -1 FeS Chemical compound 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 231100000783 metal toxicity Toxicity 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Abstract
The invention discloses a method for neutralizing mineralized acid tailings, which comprises the steps of crushing and slurrying the tailings, then aerating the slurry, adding a modifier into the aerated slurry, and uniformly stirring; according to the method, the tailings are pretreated in a crushing and pulping mode, aeration and oxygenation are carried out, oxidation of sulfides in the tailings is accelerated, and late oxidation and acid return of the tailings are prevented; then, the modifier can be added to generate a thorough neutralization reaction, so that the active acid and latent acid of the tailings can be neutralized, and the continuity of the pH of the tailings is guaranteed; the addition of the modifier can also promote heavy metal ions to form insoluble precipitates, can also wrap, adsorb and complex the precipitates, reduce the leaching rate of pollutant toxicity, can also enable fine tailing particles to be gathered into large particles, and reduce the probability of flying dust particles.
Description
Technical Field
The invention belongs to the technical field of tailing treatment, and particularly relates to a method for neutralizing and mineralizing acid tailings.
Background
The acid leachate is formed by the continuous reaction of sulfur-containing tailings and oxygen in the air under the action of rainwater, so that the pH of the tailings leachate is acidic (pH = 2-4), and sulfides in the tailings can be continuously oxidized over time, thereby continuously generating acid wastewater. Because the tailings particles are small, they are more susceptible to oxidative decomposition when exposed to air than are large rock masses. In particular, in metal sulfide mines, the pH of the wastewater may be lower due to the large amount of fine metal sulfides and elemental sulfur in the tailings. Part of sulfuric acid, such as FeS, is generated when the waste stone pyrite in the tailings is oxidized and dissolved in the leaching process2The process of oxidation dissolution in the water leaching process is as follows:
2FeS2+7O2+2H2O→2Fe2++4SO4 2-+4H+
4Fe2++O2+4H+→4Fe3++2H2O
FeS2+14Fe3++8H2O→15Fe2++2SO4 2-+16H+
the development and utilization of mineral resources are the material basis of human survival and social development, and along with the development and utilization of the mineral resources, a large amount of tailings are generated, so that serious environmental pollution can be caused due to poor treatment of the tailings. However, the environmental problems caused by the acid tailings are not inconstant, such as artificial debris flow hazard sources, chemical agent residues, underground water pollution, dust pollution, air pollution, land degradation and the like.
The most serious of the acid tailings is the harm caused by the seepage liquid, the seepage liquid is not as strong as acid and has great influence on the nearby ecological environment, and the harm of heavy metal ions in the seepage liquid to human bodies is also great. The existing acid tailing restoration method comprises an ecological restoration method (CN 107347402A) of a strong acid tailing waste land, the plant restoration period is long, and the selected plants are single; a method (CN 110369448A) for thoroughly neutralizing acid tailings and preventing continuous oxidation is capable of neutralizing the acid tailings, but has a phenomenon of acid return at a later stage and can not fix heavy metals in the tailings well. In view of the above problems, it is necessary to invent a method for neutralizing and mineralizing acid tailings.
Disclosure of Invention
The invention aims to provide a method for neutralizing and mineralizing acid tailings.
The object of the invention is achieved by a method for neutralizing mineralized acid tailings, which comprises the following steps:
s1, pulping the acid tailings to be neutralized, and crushing the tailings when the diameter of the tailings is larger than 2 mm;
s2, performing oxygen increasing aeration treatment on the pulped tailings;
and S3, adding a modifier into the aerated acid tailings, fully stirring and mixing, and reacting.
Preferably, the crushing described in S1 is to crush to particles with a particle size of more than 1mm to not more than 50%.
Preferably, the water content of the slurry in S1 is 20-30%.
Preferably, the amount of oxygen increase described in S2 is such that the oxygen content in the slurry is not less than 15 mg/L.
Preferably, the modifier described in S3 is a mixture of quicklime and kaolin.
Preferably, the modifying agent comprises the following components: the mass ratio of the kaolin is less than or equal to 3: 1.
Preferably, the addition amount of the modifying agent in the S3 is 10% of the dry mass of the acid tailings to be neutralized in the S1.
Preferably, the stirring and mixing are carried out for 10-30 min, and the reaction lasts for 7-28 days.
Preferably, the acid tailings are any one or more of a tin, copper, zinc and lead tailings pond containing metal sulfides and a waste residue storage yard containing metal sulfides.
The reaction principle of the invention is as follows:
according to the invention, sulfate radicals are generated by firstly aerating sulfides in tailings, and the reaction equation is mainly as follows:
2FeS2+7O2+2H2O→2Fe2++4SO4 2-+4H+
4Fe2++O2+4H+→4Fe3++2H2O
FeS2+14Fe3++8H2O→15Fe2++2SO4 2-+16H+
in the invention, kaolin is a fine-particle clay mineral with high aluminum content, and alumina is released from the clay mineral under an alkaline environment, and the reaction equation is as follows:
Al2SiO(OH)2.nH2O+2(OH)-+10H2O→2Al(OH)4 -+4H4SiO4+nH2O
in the invention, the sulfide in the soil after being repaired by the modifying agent finally exists underground for a long time in the form of ettringite, and the reaction equation is as follows:
6Ca(OH)2+2AlO2 -+3SO4 2-+nH2O→3CaO.Al2O3.3CaSO4.32H2O
compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the aeration operation is carried out while the neutralization reaction of the acid tailings is carried out, so that the acid tailings and the modifying agent are mixed more uniformly, and the aeration operation can quickly oxidize a large amount of metal sulfides in the acid tailings into active acids, so that the active acids are neutralized by the modifying agent, thereby realizing uniform mixing of the acid tailings and the modifying agent and complete reaction of the latent acids.
2. The method selects the mixture of the modifier quicklime and the kaolin, the quicklime can neutralize the active acid in the tailings and can precipitate the heavy metal ions in the tailings, so that the generated precipitate is contained in the tailings, and the mixture can wrap and adsorb other substances in the tailings and can inhibit the oxidation of unreacted metal sulfides.
3. The method selects the mixture of the modifier quicklime and the kaolin, the quicklime can react with the kaolin and sulfides in the soil to generate the ettringite, the ettringite can wrap, adsorb and complex various substances in the tailings, the leaching of heavy metal toxicity is reduced, fine tailing particles can be gathered into large particles, the dust flying caused by the small particles is prevented, and the ettringite also has the effects of water retention and fertilizer retention.
4. The method selects the mixture of the quicklime and the kaolin as the modifier, the formation of the ettringite can be accelerated by the existence of the kaolin, and the formation of the ettringite can cause the modified soil body to properly expand and reduce the permeability coefficient of the soil, thereby weakening the migration of pollutants.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
Example 1
A method for neutralizing mineralized acid tailings, comprising the following steps:
s1, directly pulping the acid tailings meeting the particle size requirement, wherein the water content of the pulping liquid is 20%;
s2, adding a modifier into the acid tailing slurry, wherein the weight ratio of quicklime: kaolin =2:1, total modifier mass: the mass of the dry acid tailings is = 10%, and the dry acid tailings are uniformly stirred;
s3, carrying out aeration treatment while the reaction is carried out, and increasing the dissolved oxygen of the solution to 15 mg/L.
Example 2
A method for neutralizing mineralized acid tailings comprises the following steps:
s1, crushing and slurrying the acid tailings; wherein the tailings are crushed into 50% particles with the particle size larger than 1mm, and the water content of the tailing slurry is 25%;
s2, adding a modifier into the acid tailing slurry, wherein the weight ratio of quicklime: kaolin =2:1, total modifier mass: the dry soil mass = 10%, and the mixture is stirred uniformly;
s3, stirring for 20min without aeration while the neutralization reaction is carried out.
Example 3
A method for neutralizing and mineralizing acid tailings comprises the following steps:
s1, crushing and slurrying the acid tailings; 50% of particles with the crushed particle size of the tailings being more than 1mm, and the water content of the tailing slurry liquid being 25%;
s2, adding a modifier into the acid tailing slurry, wherein the weight ratio of quicklime: kaolin =2.5:1, total modifier mass: the dry soil mass = 10%, and the mixture is stirred uniformly;
s3, carrying out aeration treatment while the reaction is carried out, and increasing the dissolved oxygen of the solution to 20 mg/L.
Example 4
A method for neutralizing acid tailings comprises the following steps:
s1, crushing and slurrying the acid tailings; the crushed particles with the particle size of more than 1mm of the tailings are not higher than 50 percent, and the water content of the tailing slurry is 25 percent;
s2, adding quicklime into the acid tailing slurry, wherein the adding amount of the quicklime is as follows: the dry soil mass = 10%, and the mixture is stirred uniformly;
s3, carrying out aeration treatment while the reaction is carried out, and increasing oxygen until the dissolved oxygen content of the solution is 25 mg/L.
Example 5
A method for neutralizing and mineralizing acid tailings comprises the following steps:
s1, crushing and slurrying the acid tailings; the crushed particles with the particle size of more than 1mm of the tailings are not higher than 50 percent, and the water content of the tailing slurry is 25 percent;
s2, adding a modifier into the acid tailing slurry, wherein the weight ratio of quicklime: kaolin =2:1, total modifier mass: the mass of the dry soil (the mass of the dry acid tailings) = 10%, and the materials are uniformly stirred;
and S3, carrying out aeration treatment while carrying out reaction, increasing oxygen until the dissolved oxygen content of the solution is 15 mg/L, fully stirring and mixing for 20min, reacting for 7 days, and generating ettringite precipitate to coat the tailing pond.
The acid tailings of the embodiments 1 to 5 belong to lead tailings, and sulfur elements in the tailings are easily oxidized by air and react with moisture in the environment to generate sulfuric acid to form acid leachate.
The following table shows the data measured in the examples:
TABLE 1 results of examples 1 to 5
As shown in Table 1, the pH change of the tailings treated by the method is obvious, the acid returning phenomenon of example 2 is obvious, and the aeration effect of the method is obvious; according to the toxic leaching data, the effect comparison of the modifier addition can be seen, the effect of only adding quicklime without the modifier has a certain effect on the pH value of the tailings, but the fixing effect on heavy metals is not obvious, and the method for neutralizing and mineralizing the acidic tailings has an obvious effect.
Claims (9)
1. A method for neutralizing mineralized acid tailings is characterized by comprising the following steps:
s1, pulping the acid tailings to be neutralized, and crushing the tailings when the diameter of the tailings is larger than 2 mm;
s2, performing oxygen increasing aeration treatment on the pulped tailings;
and S3, adding a modifier into the aerated acid tailings, fully stirring and mixing, and reacting.
2. The process of neutralising mineralized acid tailings according to claim 1, wherein the fragmentation in S1 is to break up to particles with a size greater than 1mm not greater than 50%.
3. The method for neutralizing mineralized acid tailings according to claim 1, wherein the water content of the slurry solution in the S1 is 20-30%.
4. The method for neutralizing mineralized acid tailings according to claim 1, wherein the oxygen increase amount in the S2 is to keep the oxygen content in the slurry liquid not lower than 15 mg/L.
5. The process of neutralizing mineralized acid tailings according to claim 1, wherein the modifier in S3 is a mixture of quicklime and kaolin.
6. The method for neutralizing mineralized acid tailings according to claim 5, wherein the ratio of quicklime to quicklime in the improver: the mass ratio of the kaolin is less than or equal to 3: 1.
7. The method for neutralizing mineralized acid tailings according to claim 1, wherein the amount of modifier added is 10% of the dry mass of the acid tailings to be neutralized.
8. The method for neutralizing mineralized acid tailings according to claim 1, wherein the stirring and mixing are performed for 10-30 min, and the reaction lasts for 7-28 days.
9. The method for neutralizing mineralized acid tailings according to claim 1, wherein the acid tailings are metal sulfide-containing tin, copper, zinc, lead tailings ponds or metal sulfide-containing waste dump sites.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010262226.4A CN111389866A (en) | 2020-04-06 | 2020-04-06 | Method for neutralizing and mineralizing acid tailings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010262226.4A CN111389866A (en) | 2020-04-06 | 2020-04-06 | Method for neutralizing and mineralizing acid tailings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111389866A true CN111389866A (en) | 2020-07-10 |
Family
ID=71417469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010262226.4A Pending CN111389866A (en) | 2020-04-06 | 2020-04-06 | Method for neutralizing and mineralizing acid tailings |
Country Status (1)
| Country | Link |
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| CN (1) | CN111389866A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457269A (en) * | 1992-09-08 | 1995-10-10 | Zapit Technology, Inc. | Oxidizing enhancement electron beam process and apparatus for contaminant treatment |
| CN103073255A (en) * | 2012-12-13 | 2013-05-01 | 河南理工大学 | Production method of hole sealing material for gas drainage hole |
| CN103695670A (en) * | 2013-11-21 | 2014-04-02 | 南昌大学 | Method for improving ionic rare earth extraction rate and mine tailing safety |
| CN105601051A (en) * | 2016-03-11 | 2016-05-25 | 山西农业大学 | Biomineralization-based acidic mine wastewater treatment system and treatment method |
| CN110369448A (en) * | 2019-07-15 | 2019-10-25 | 昆明理工大学 | A kind of thorough method for neutralizing acid tailing and preventing continued oxidation |
-
2020
- 2020-04-06 CN CN202010262226.4A patent/CN111389866A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457269A (en) * | 1992-09-08 | 1995-10-10 | Zapit Technology, Inc. | Oxidizing enhancement electron beam process and apparatus for contaminant treatment |
| CN103073255A (en) * | 2012-12-13 | 2013-05-01 | 河南理工大学 | Production method of hole sealing material for gas drainage hole |
| CN103695670A (en) * | 2013-11-21 | 2014-04-02 | 南昌大学 | Method for improving ionic rare earth extraction rate and mine tailing safety |
| CN105601051A (en) * | 2016-03-11 | 2016-05-25 | 山西农业大学 | Biomineralization-based acidic mine wastewater treatment system and treatment method |
| CN110369448A (en) * | 2019-07-15 | 2019-10-25 | 昆明理工大学 | A kind of thorough method for neutralizing acid tailing and preventing continued oxidation |
Non-Patent Citations (1)
| Title |
|---|
| 马清浩，杭美艳: "《水泥混凝土外加剂550问》", 30 November 2008, 中国建材工业出版社 * |
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Application publication date: 20200710 |