CN115093168A - Method for fixing arsenic in tin tailings by using cement - Google Patents
Method for fixing arsenic in tin tailings by using cement Download PDFInfo
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- CN115093168A CN115093168A CN202210717514.3A CN202210717514A CN115093168A CN 115093168 A CN115093168 A CN 115093168A CN 202210717514 A CN202210717514 A CN 202210717514A CN 115093168 A CN115093168 A CN 115093168A
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- cement
- tin
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- 239000004568 cement Substances 0.000 title claims abstract description 65
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 48
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims description 10
- 230000036571 hydration Effects 0.000 abstract description 7
- 238000006703 hydration reaction Methods 0.000 abstract description 7
- 229940000489 arsenate Drugs 0.000 abstract description 5
- 229910001653 ettringite Inorganic materials 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 230000001988 toxicity Effects 0.000 description 9
- 231100000419 toxicity Toxicity 0.000 description 9
- 229920000876 geopolymer Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 arsenate ions Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 238000001134 F-test Methods 0.000 description 1
- AGWMJKGGLUJAPB-UHFFFAOYSA-N aluminum;dicalcium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Ca+2].[Ca+2].[Fe+3] AGWMJKGGLUJAPB-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a method for fixing arsenic in tin tailings by using cement, and belongs to the technical field of hydrometallurgy. The method comprises the steps of respectively grinding, screening and drying tin tailings and cement to obtain tin tailing powder and cement powder; uniformly mixing tin tailing powder and cement powder to obtain a mixture A; adding water into the mixture A, and uniformly mixing to obtain slurry B; and injecting the slurry B into a mold, sealing and standing for 24-48 h at room temperature, demolding, and curing for more than 3d at room temperature and under the condition that the humidity is 90-95% to obtain the arsenic-containing solid. In the process of forming a three-dimensional network structure by water excitation, the cement is beneficial to forming C-S-H gel which is filled in gaps among hydration products, so that the compactness of the structure is improved, As element enters a main body structure of the C-S-H gel to fix the As element, and the compressive strength is improved; the ettringite containing arsenate radical has expansibility, can reduce the porosity of the coating body and improve the compactness of the structure.
Description
Technical Field
The invention relates to a method for fixing arsenic in tin tailings by using cement, and belongs to the technical field of hydrometallurgy.
Background
The tin tailings are mainly in an amorphous state, the main crystalline minerals are calcite, quartz and fluorite, most of the crystalline minerals exist in a blocky state, and the surfaces of the crystalline minerals are smooth and compact.
The arsenate ions in the tin tailings and dicalcium silicate, tricalcium aluminate and tetracalcium aluminoferrite generated in the cement hydration process perform chemical reaction to perform ion exchange, and are condensed into a whole, and the arsenate ions are fixed. The cement hydration process is alkaline, and the reaction is promoted to occur. The C-S-H gel and ettringite formed by cement can make the three-dimensional network structure formed by hydration more compact, the arsenic ions are fixed by physical coating, and the physical and chemical reactions are carried out simultaneously.
The existing arsenic fixing method is mainly a chemical precipitation method, but the arsenic-containing precipitate generated by precipitation has poor stability, high solubility, high leaching toxicity concentration of arsenic, easy secondary pollution and incapability of meeting the requirement of stable arsenic fixing.
Disclosure of Invention
The invention provides a method for fixing arsenic in tin tailings by using cement, aiming at the problem of arsenic treatment in the existing tin tailings, namely, the cement is used for forming a three-dimensional network structure in a water excitation process, so that C-S-H gel is favorably formed, the C-S-H gel is filled in gaps among hydration products, the compactness of the structure is improved, As element enters a main body structure of the C-S-H gel to fix As element, and the compressive strength is improved; the ettringite containing arsenate radicals has expansibility, can reduce the porosity of the coating body and improve the compactness of the structure.
A method for fixing arsenic in tin tailings by using cement comprises the following specific steps:
(1) respectively grinding, sieving and drying the tin tailings and the cement to obtain tin tailing powder and cement powder;
(2) uniformly mixing tin tailing powder and cement powder to obtain a mixture A;
(3) adding water into the mixture A, and uniformly mixing to obtain slurry B;
(4) and injecting the slurry B into a mold, sealing and standing for 24-48 h at room temperature, demolding, and curing for more than 3d at room temperature and under the condition that the humidity is 90-95% to obtain the arsenic-containing solid.
And (3) in the mixture A in the step (2), the cement accounts for 30-60 wt%, and the balance is tin tailing powder.
And (4) the water-cement ratio of the slurry B in the step (3) is 0.3-0.6.
And (3) testing the compressive strength and arsenic concentration of the arsenic-containing solid, namely testing the compressive strength of the test block cured to the corresponding age, then testing leaching, and detecting the concentration of arsenic in the leachate by using an Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES).
The principle of cement arsenic fixation: stabilizing and solidifying arsenic in the tin tailings by using cement, and reducing the leaching concentration of the arsenic to a safe range; during the stable solidification treatment, OH-generated by cement hydration promotes the breakage of As (III) -S bonds and Fe-As (V) bonds and Ca 2+ Form Ca-As (V) precipitate, and amorphous As (III) -O bond with Ca 2+ Ca-As (III) bond precipitation is formed, and the dissolved As (III) is oxidized to increase As (V); the cement hydration product C-S-H and the ettringite containing arsenate radical also reach the effect of stabilizing and solidifying As through adsorption and ion exchange.
The beneficial effects of the invention are:
(1) the cement arsenic fixation agent effectively utilizes cement arsenic fixation, As participates in reaction in the reaction process, and the arsenic fixation agent is integrated with geopolymer, and has high compressive strength and extremely low arsenic leaching rate;
(2) the arsenic-containing solid has excellent compressive strength, the compressive strength can reach 22.76MPa in 3 days, 26.38MPa in 7 days and 37.36MPa in 28 days;
(3) the invention has simple process flow and convenient operation flow, is used for forming a compact structure to achieve the aim of fixing the heavy metal arsenic, has the fixing effect which can meet the standard of national standard leaching, has high strength, and can be used as a road paving material for rural roads.
Drawings
FIG. 1 is a bar graph of compressive strength of arsenic-containing solids after 3, 7 and 28 days of curing in examples 1-4;
FIG. 2 is a bar graph of the leaching efficiency and pH of arsenic-containing solids after 28 days of curing in examples 1-4.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: the tin tailings adopted in the embodiment are taken from old cities of Yunnan province, and the composition of the components is shown in table 1; the cement is from a cement plant in Hunan, and the composition is shown in Table 2;
TABLE 1 tin tailing composition (wt%)
TABLE 2 Cement Components composition (wt%)
A method for fixing arsenic in tin tailings by using cement comprises the following specific steps:
(1) grinding the tin tailings for 2 hours, sieving by a 180-mesh sieve, and drying at the temperature of 60 ℃ to obtain tin tailing powder, and grinding cement for 2 hours, sieving, and drying at the temperature of 60 ℃ to obtain cement powder;
(2) uniformly mixing tin tailing powder and cement powder to obtain a mixture A; wherein the cement powder in mixture a is 30 wt.%;
(3) adding water into the mixture A, and uniformly mixing to obtain slurry B; wherein the ratio of water to ash in the slurry B is 0.3;
(4) injecting the slurry B into a mold, sealing and standing for 24h at room temperature, demolding, and maintaining for more than 3d at room temperature and at the humidity of 90% to obtain arsenic-containing solid A1;
performance testing the following methods were used to test the compressive strength: taking out the sample reaching the specified maintenance time, placing the sample on a compressive strength testing machine, taking the side surface of the test piece during molding as a pressure-bearing surface, placing the test piece on a lower pressing plate or a base plate of the testing machine, aligning the center of the test piece with the center of the lower pressing plate of the testing machine, starting the machine, reading out the compressive strength readings on a screen, and testing 3 average values of each group of samples;
and (3) calculating test results:
f＝F/A
f-cube test piece compressive strength (MPa)
F-test piece breaking load (N)
A-test piece pressure bearing area (mm) 2 )
The compressive strength of the cubic sample is calculated to be accurate to 0.1 MPa;
the Toxicity Leaching test was performed according to U.S. epa standard Method 1311 proximity charaterisitc leach Procedure as promulgated by the united states environmental protection agency;
the compressive strength of the arsenic-containing solid in this example is shown in FIG. 1, the compressive strength is 11.25MPa in 3 days, 16.83MPa in 7 days, 18.92MPa in 28 days, and the arsenic leaching concentration is 0.12mg/L as shown in FIG. 2. It can be seen that the intensity of geopolymer is increased with time, the leaching toxicity is less than 5mg/L, and the national standard is met.
Example 2: the tin tailings adopted in the embodiment are taken from old cities of Yunnan province, and the composition of the components is shown in table 3; the cement is from a cement plant in Hunan, and the composition is shown in Table 4;
TABLE 3 tin tailing composition (wt%)
TABLE 4 Cement Components composition (wt%)
A method for fixing arsenic in tin tailings by using cement comprises the following specific steps:
(1) grinding the tin tailings for 3 hours, sieving by a 180-mesh sieve, drying at the temperature of 65 ℃ to obtain tin tailing powder, grinding cement for 2.5 hours, sieving, and drying at the temperature of 70 ℃ to obtain cement powder;
(2) uniformly mixing tin tailing powder and cement powder to obtain a mixture A; wherein the cement powder in mixture a comprises 40 wt.%;
(3) adding water into the mixture A, and uniformly mixing to obtain slurry B; wherein the ratio of water to ash in the slurry B is 0.4;
(4) injecting the slurry B into a mold, sealing and standing for 30h at room temperature, demolding, and maintaining for more than 3d at room temperature and under the humidity of 92% to obtain arsenic-containing solid A2;
the performance test and toxicity leaching test methods were the same as in example 1;
the compressive strength of the arsenic-containing solid in this example is shown in FIG. 1, the compressive strength is 14.52MPa in 3 days, 18.92MPa in 7 days, 25.38MPa in 28 days, and the arsenic leaching concentration is 0.73mg/L as shown in FIG. 2. It can be seen that the intensity of geopolymer is increased with time, the leaching toxicity is less than 5mg/L, and the national standard is met.
Example 3: the tin tailings adopted in the embodiment are taken from old cities of Yunnan province, and the composition of the components is shown in table 5; the cement is from a certain cement plant in Hunan province, and the composition is shown in Table 6;
TABLE 5 tin tailing composition (wt%)
TABLE 6 Cement constituent composition (wt%)
A method for fixing arsenic in tin tailings by using cement comprises the following specific steps:
(1) grinding the tin tailings for 2.5h, sieving by a 180-mesh sieve, and drying at the temperature of 70 ℃ to obtain tin tailing powder, grinding cement for 3h, sieving, and drying at the temperature of 60 ℃ to obtain cement powder;
(2) uniformly mixing tin tailing powder and cement powder to obtain a mixture A; wherein the cement powder in mixture a comprises 50 wt.%;
(3) adding water into the mixture A, and uniformly mixing to obtain slurry B; wherein the ratio of water to ash in the slurry B is 0.5;
(4) injecting the slurry B into a mold, sealing and standing for 36h at room temperature, demolding, and maintaining for more than 3d at room temperature and with the humidity of 93% to obtain arsenic-containing solid A3;
the performance test and toxicity leaching test methods were the same as in example 1;
the compressive strength of the arsenic-containing solid of this example is shown in FIG. 1, the compressive strength is 17.11MPa in 3 days, 21.35MPa in 7 days, 27.36MPa in 28 days, and the arsenic leaching concentration is 0.56mg/L as shown in FIG. 2. It can be seen that the intensity of geopolymer is increased with time, the leaching toxicity is less than 5mg/L, and the national standard is met.
Example 4: the tin tailings adopted in the embodiment are taken from old cities of Yunnan province, and the composition of the components is shown in table 7; the cement is from a cement plant in Hunan province, and the composition is shown in Table 8;
TABLE 7 tin tailing composition (wt%)
TABLE 8 Cement component composition (wt%)
A method for fixing arsenic in tin tailings by using cement comprises the following specific steps:
(1) grinding the tin tailings for 2 hours, sieving the ground tin tailings by a 180-mesh sieve, and drying at the temperature of 65 ℃ to obtain tin tailing powder, grinding cement for 3 hours, sieving the ground tin tailing powder, and drying at the temperature of 65 ℃ to obtain cement powder;
(2) uniformly mixing tin tailing powder and cement powder to obtain a mixture A; wherein the cement powder in mixture a is 60 wt.%;
(3) adding water into the mixture A, and uniformly mixing to obtain slurry B; wherein the ratio of water to ash in the slurry B is 0.6;
(4) injecting the slurry B into a mold, sealing and standing for 48h at room temperature, demolding, and maintaining for more than 3d at room temperature and at the humidity of 95% to obtain arsenic-containing solid A4;
the performance test and toxicity leaching test methods were the same as in example 1;
the compressive strength of the arsenic-containing solid of this example is shown in FIG. 1, the compressive strength is 22.76MPa for 3 days, 26.38MPa for 7 days, 37.36MPa for 28 days, and the arsenic leaching concentration is 0.05mg/L as shown in FIG. 2. It can be seen that the intensity of geopolymer is increased with time, the leaching toxicity is less than 5mg/L, and the geopolymer meets the national standard.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (3)
1. A method for fixing arsenic in tin tailings by using cement is characterized by comprising the following steps: the method comprises the following specific steps:
(1) respectively grinding, sieving and drying the tin tailings and the cement to obtain tin tailing powder and cement powder;
(2) uniformly mixing tin tailing powder and cement powder to obtain a mixture A;
(3) adding water into the mixture A, and uniformly mixing to obtain slurry B;
(4) and injecting the slurry B into a mold, sealing and standing for 24-48 h at room temperature, demolding, and curing for more than 3d at room temperature and under the condition that the humidity is 90-95% to obtain the arsenic-containing solid.
2. The method for fixing arsenic in tin tailings by using cement as claimed in claim 1, wherein the method comprises the following steps: in the mixture A in the step (2), 30-60 wt% of cement is contained, and the balance is tin tailing powder.
3. The method for fixing arsenic in tin tailings by using cement as claimed in claim 1, wherein the method comprises the following steps: and (4) the water-cement ratio of the slurry B in the step (3) is 0.3-0.6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210717514.3A CN115093168A (en) | 2022-06-23 | 2022-06-23 | Method for fixing arsenic in tin tailings by using cement |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210717514.3A CN115093168A (en) | 2022-06-23 | 2022-06-23 | Method for fixing arsenic in tin tailings by using cement |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218428A (en) * | 2011-01-20 | 2011-10-19 | 杭州大地环保有限公司 | Treatment method of arsenic slag |
| CN102249609A (en) * | 2011-04-29 | 2011-11-23 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
| CN108774024A (en) * | 2018-06-08 | 2018-11-09 | 东莞理工学院 | A kind of method of arsenic slag firming body and arsenic slag solidification and stabilization |
| CN109570183A (en) * | 2018-10-12 | 2019-04-05 | 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) | A kind of method of arsenic-containing waste residue solidification and stabilization processing |
-
2022
- 2022-06-23 CN CN202210717514.3A patent/CN115093168A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218428A (en) * | 2011-01-20 | 2011-10-19 | 杭州大地环保有限公司 | Treatment method of arsenic slag |
| CN102249609A (en) * | 2011-04-29 | 2011-11-23 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
| CN108774024A (en) * | 2018-06-08 | 2018-11-09 | 东莞理工学院 | A kind of method of arsenic slag firming body and arsenic slag solidification and stabilization |
| CN109570183A (en) * | 2018-10-12 | 2019-04-05 | 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) | A kind of method of arsenic-containing waste residue solidification and stabilization processing |
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| Title |
|---|
| W.-H. CHOI等: "Cement based solidification/stabilization of arsenic-contaminated mine tailings", 《WASTE MANAGEMENT》, pages 1766 - 1771 * |
| 吴文卫等: "《典型砷污染地块修复治理技术及应用》", 30 June 2020, 冶金工业出版社, pages: 31 * |
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