CN110845100A - Method for targeting arsenic fixation of fly ash synergistic stabilization medicament - Google Patents
Method for targeting arsenic fixation of fly ash synergistic stabilization medicament Download PDFInfo
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- CN110845100A CN110845100A CN201911049108.9A CN201911049108A CN110845100A CN 110845100 A CN110845100 A CN 110845100A CN 201911049108 A CN201911049108 A CN 201911049108A CN 110845100 A CN110845100 A CN 110845100A
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- arsenic
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 76
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000010881 fly ash Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003814 drug Substances 0.000 title claims abstract description 16
- 230000008685 targeting Effects 0.000 title claims abstract description 15
- 230000006641 stabilisation Effects 0.000 title claims abstract description 14
- 238000011105 stabilization Methods 0.000 title claims abstract description 14
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000003381 stabilizer Substances 0.000 claims abstract description 39
- 239000010802 sludge Substances 0.000 claims abstract description 37
- 239000004568 cement Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011398 Portland cement Substances 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 description 18
- 230000001988 toxicity Effects 0.000 description 15
- 231100000419 toxicity Toxicity 0.000 description 15
- 239000011083 cement mortar Substances 0.000 description 9
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- -1 arsenic ions Chemical class 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 231100000820 toxicity test Toxicity 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 208000007443 Neurasthenia Diseases 0.000 description 1
- 206010036105 Polyneuropathy Diseases 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000007824 polyneuropathy Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Abstract
The invention relates to a method for targeting arsenic fixation by a synergistic stabilization medicament of fly ash, belonging to the technical field of heavy metal pollution treatment. According to the invention, Portland cement and fly ash are added into arsenic-containing sludge and uniformly mixed to obtain a mixture A; adding a stabilizing agent into the mixture A and uniformly mixing to obtain a mixture B; under the stirring condition, adding the mixture B into water, uniformly mixing to obtain cement paste, and aging the cement paste for 40-60 min; and pouring the aged cement paste into a mold for molding, demolding the molded block, and naturally curing for 7-28 days to obtain the harmless cured block. The fly ash in the invention can be used as an accelerant in the arsenic curing process to enhance the compressive strength of the cured block; the stabilizing agent can be used for pertinently fixing arsenic and improving the stability of the arsenic-containing sludge.
Description
Technical Field
The invention relates to a method for targeting arsenic fixation by a synergistic stabilization medicament of fly ash, belonging to the technical field of heavy metal pollution treatment.
Background
Arsenic is a metal-like substance and can form a series of highly toxic compounds, the arsenic can be absorbed by human bodies from respiratory tracts, skins and digestive tracts and can cause neurasthenia syndrome, polyneuropathy, skin mucosa lesion and the like, and inorganic compounds of the arsenic can cause lung cancer and skin cancer. After arsenic-containing wastewater is treated, most harmful substances such as arsenic are transferred into sludge, so that the method has important practical significance for safe treatment and disposal research of the arsenic-containing sludge.
Disclosure of Invention
The invention provides a method for targeting arsenic fixation by using fly ash and a stabilizing agent, aiming at the problems in the prior art, the fly ash and the stabilizing agent are utilized to promote the solidification of arsenic-containing sludge, the fly ash is beneficial to pouring and molding and replaces cement to reduce the production cost, the fly ash is used as an accelerant in the arsenic solidification process, the compressive strength of a solidified block is greatly improved, the stabilizing agent targets arsenic fixation, the stability of the arsenic-containing sludge is enhanced, and the diffusion and harm of arsenic in the environment are reduced.
The invention can improve the fluidity, cohesiveness and water-retaining property of the concrete by adding a proper amount of fly ash into the cement, so that the concrete mixture is easy to pump and pour for molding. The cement consumption can be reduced after the fly ash is added, and the hydration heat release of the fly ash is little, so that the hydration heat release is reduced; the addition of the fly ash can reduce the cement consumption by about 10-15% under the condition of equal strength grade, and reduce the experiment cost;
the stabilizing agent of the present invention is mainly used for treating heavy metal waste, and the main mechanisms of the stabilizing agent are the chemical bond binding force between the waste and the coagulant, the physical containment of the coagulant on the waste and the adsorption of the coagulant hydration product on the waste. The hazardous waste is treated by the stabilizing medicament technology, so that the waste can be harmlessly treated, and the waste can be slightly increased or not increased, thereby improving the overall efficiency and the economy of the hazardous waste treatment and disposal system.
A method for targeting arsenic fixation of a fly ash synergistic stabilization medicament comprises the following specific steps:
(1) adding portland cement and fly ash into arsenic-containing sludge, and uniformly mixing to obtain a mixture A;
(2) adding a stabilizing agent into the mixture A obtained in the step (1) and uniformly mixing to obtain a mixture B;
(3) under the stirring condition, adding the mixture B in the step (2) into water, uniformly mixing to obtain cement paste, and carrying out aging treatment on the cement paste for 40-60 min;
(4) and (4) pouring the cement paste subjected to the aging treatment in the step (3) into a mould for forming, and naturally curing the formed block for 7-28 days after demoulding to obtain the harmless cured block.
The mass ratio of the portland cement, the fly ash and the arsenic-containing sludge in the step (1) is (1:1:2) - (2:2: 3).
The arsenic content of the arsenic-containing sludge in the step (1) is 105-136 mg/L.
The stabilizing agents in the step (2) are CaO and SiO2MgO and Al2O3Wherein the CaO concentration in the stabilizing agent is 4-5 mg/L, SiO23-4 mg/L, MgO concentration of 1-1.2 mg/L and Al2O3The concentration is 1.2-1.4 mg/L, and the liquid-solid ratio mL of the stabilizing agent to the mixture B is (0.1-0.3): 1.
And (3) the aging temperature is 40-50 ℃.
The principle of targeting arsenic fixation of the fly ash synergistic stabilization medicament is as follows: the main component of the fly ash is SiO2The stabilizing agent is mainly CaO and contains Mg, Si, Al and other components, Si in the fly ash and Ca in the agent are subjected to condensation reaction under an alkaline condition to produce C-S-H gel, and the gel can tightly wrap As-containing sludge, reduce the migration capacity and leaching toxicity of the As-containing sludge and play a role in stabilizing harmful pollutants.
The invention has the beneficial effects that:
the invention utilizes the fly ash and the stabilizing agent to promote the solidification of the arsenic-containing sludge, the fly ash can effectively replace part of expensive cement, and the proper amount of fly ash is added into the cement to improve the fluidity, cohesiveness and water-retaining property of the arsenic-containing mixture, so that the arsenic-containing mixture is easier to pour and mold; the compression strength of the solidified block can be effectively improved by the fly ash; the substances lacking in the stabilizing agent during the targeted addition and solidification can enhance the stability of the arsenic-containing sludge and reduce the diffusion and harm of arsenic in the environment.
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: in the embodiment, the cement components are shown in table 1, the fly ash components are shown in table 2, the stabilizing agent is shown in table 3, the arsenic-containing sludge is sludge obtained by removing arsenic in wastewater by a lime neutralization precipitation method in a sulfuric acid plant of a certain zinc smelting plant in the southwest region, and the main components are shown in table 4;
a method for targeting arsenic fixation of a fly ash synergistic stabilization medicament comprises the following specific steps:
(1) adding portland cement and fly ash into arsenic-containing sludge, and uniformly mixing to obtain a mixture A; wherein the mass ratio of the portland cement to the fly ash to the arsenic-containing sludge is 1:1: 2; the arsenic content of the sludge is 105 mg/L;
(2) adding a stabilizing agent into the mixture A obtained in the step (1) and uniformly mixing to obtain a mixture B; wherein the stabilizing agent is CaO or SiO2MgO and Al2O3Wherein the CaO concentration in the stabilizing agent is 4 mg/L, SiO2Concentration 4 mg/L, MgO concentration 1 mg/L and Al2O3The concentration is 1.2 mg/L, and the liquid-solid ratio mL: g of the stabilizing agent to the mixture B is 0.1: 1;
(3) adding the mixture B and water in the step (2) into a cement mortar stirrer, stirring the mixture B and the water in the cement mortar stirrer, uniformly mixing the mixture B and the water to obtain cement paste, and aging the cement paste for 60min at the temperature of 50 ℃; wherein the mass ratio of the mixture B to water is 1:0.3, and the stirring speed of the cement mortar stirrer is 50 r/min;
(4) pouring the cement paste subjected to aging treatment in the step (3) into a mould for forming, and naturally curing the formed block for 28 days after demoulding to obtain a harmless cured block;
toxicity Leaching tests of arsenic-containing solids were performed according to U.S. epa Method 1311-toxicitycharateristic leach Procedure, provided by the united states environmental protection agency, with toxicity test results as shown in table 5,
TABLE 5 compression Strength and toxicity Leaching results for arsenic-containing cured blocks
As can be seen from Table 5, when the mass ratio of the portland cement to the fly ash to the arsenic-containing sludge is 1:1:2, and the liquid-solid ratio mL: g of the stabilizing agent to the mixture B is 0.1:1, the compressive strengths of the mixture after natural curing for 7 days, 14 days and 28 days are 31.28 MPa, 35.89 MPa and 52.23 MPa respectively, and the addition of the fly ash and the stabilizing agent has a strong accelerating effect on the solidification of the arsenic-containing sludge compared with the addition of 20 MPa in the literature; the leaching concentrations of the arsenic ions are 3.901 mg/L, 2.813 mg/L and 2.502 mg/L respectively, and it can be seen that the leaching toxicity of the arsenic is continuously reduced along with the prolonging of the time, and the leaching toxicity is less than 5mg/L, which meets the national standard.
Example 2: in this example, the cement components are shown in table 6, the fly ash components are shown in table 7, the stabilizing agent is shown in table 8, the arsenic-containing sludge is obtained from a sludge obtained by removing arsenic from wastewater by a lime neutralization precipitation method in a sulfuric acid plant of a certain zinc smelting plant in the southwest region, and the main components are shown in table 9;
a method for targeting arsenic fixation of a fly ash synergistic stabilization medicament comprises the following specific steps:
(1) adding portland cement and fly ash into arsenic-containing sludge, and uniformly mixing to obtain a mixture A; wherein the mass ratio of the portland cement to the fly ash to the arsenic-containing sludge is 2:2: 3; the arsenic content of the sludge is 136 mg/L;
(2) adding a stabilizing agent into the mixture A in the step (1)Mixing the medicaments uniformly to obtain a mixture B; wherein the stabilizing agent is CaO or SiO2MgO and Al2O3Wherein the CaO concentration in the stabilizing agent is 5mg/L, SiO2Concentration of 3 mg/L, MgO concentration of 1.2 mg/L and Al2O3The concentration is 1.4 mg/L, and the liquid-solid ratio mL: g of the stabilizing agent to the mixture B is 0.3: 1;
(3) adding the mixture B and water in the step (2) into a cement mortar stirrer, stirring the mixture B and the water in the cement mortar stirrer, uniformly mixing the mixture B and the water to obtain cement paste, and aging the cement paste for 40min at the temperature of 40 ℃; wherein the mass ratio of the mixture B to water is 1:0.5, and the stirring speed of the cement mortar stirrer is 90 r/min;
(4) pouring the cement paste subjected to aging treatment in the step (3) into a mould for forming, and naturally curing the formed block for 28 days after demoulding to obtain a harmless cured block;
respectively testing the compressive strength and leaching toxicity of the cured blocks in the natural curing stages 7, 14 and 28 d;
toxicity Leaching test of arsenic-containing solidified blocks was carried out according to U.S. epa Method 1311-toxicitycharateristic leach Procedure provided by the united states environmental protection agency, the results of compressive strength and toxicity test are shown in table 10,
TABLE 10 compression Strength and toxicity Leaching results for arsenic-containing cured blocks
As can be seen from table 10, when the mass ratio of the portland cement to the fly ash to the arsenic-containing sludge is 2:2:3, and the liquid-solid ratio mL: g of the stabilizing agent to the mixture B is 0.3:1, the compressive strengths of the mixture after natural curing for 7 days, 14 days and 28 days are 37.25 MPa, 44.16 MPa and 53.98 MPa, respectively, and the addition of the fly ash and the stabilizing agent has a strong accelerating effect on the solidification of the arsenic-containing sludge compared with 20 MPa in the literature; the leaching concentrations of arsenic ions are 2.771 mg/L, 2.015 mg/L and 1.557 mg/L respectively, and it can be seen that the leaching toxicity of arsenic is continuously reduced along with the prolonging of time, and the leaching toxicity is less than 5mg/L, which meets the national standard.
Example 3: in this example, the cement components are shown in table 11, the fly ash components are shown in table 12, the stabilizing agent is shown in table 13, the arsenic-containing sludge is obtained from a sludge obtained by removing arsenic from wastewater by lime neutralization precipitation in a sulfuric acid plant of a certain zinc smelting plant in the southwest region, and the main components are shown in table 14;
a method for targeting arsenic fixation of a fly ash synergistic stabilization medicament comprises the following specific steps:
(1) adding portland cement and fly ash into arsenic-containing sludge, and uniformly mixing to obtain a mixture A; wherein the mass ratio of the portland cement to the fly ash to the arsenic-containing sludge is 1.5:1.5: 2.5; the arsenic content of the sludge is 120.7 mg/L;
(2) adding a stabilizing agent into the mixture A obtained in the step (1) and uniformly mixing to obtain a mixture B; wherein the stabilizing agent is CaO or SiO2MgO and Al2O3Wherein the CaO concentration in the stabilizing agent is 4.5 mg/L, SiO2Concentration of 3.5mg/L, MgO concentration of 1.1 mg/L and Al2O3The concentration is 1.3 mg/L, and the liquid-solid ratio mL: g of the stabilizing agent to the mixture B is 0.2: 1;
(3) adding the mixture B and water in the step (2) into a cement mortar stirrer, stirring the mixture B and the water in the cement mortar stirrer, uniformly mixing the mixture B and the water to obtain cement paste, and aging the cement paste for 40min at the temperature of 40 ℃; wherein the mass ratio of the mixture B to water is 1:0.4, and the stirring speed of the cement mortar stirrer is 70 r/min;
(4) pouring the cement paste subjected to aging treatment in the step (3) into a mould for forming, and naturally curing the formed block for 28 days after demoulding to obtain a harmless cured block;
respectively testing the compressive strength and leaching toxicity of the cured blocks in the natural curing stages 7, 14 and 28 d;
toxicity Leaching test of arsenic-containing solidified blocks was carried out according to U.S. epa Method 1311-toxicitycharateristic leach Procedure provided by the united states environmental protection agency, and the results of the compressive strength and toxicity test are shown in table 15,
TABLE 15 compression Strength and toxicity Leaching results for arsenic-containing cured blocks
As can be seen from table 15, when the mass ratio of the portland cement, the fly ash and the arsenic-containing sludge is 1.5:1.5:2.5, and the liquid-solid ratio mL: g of the stabilizing agent to the mixture B is 0.2:1, the compressive strengths of the mixture after natural curing for 7 days, 14 days and 28 days are 40.01MPa, 47.34 MPa and 58.02 MPa, respectively, and the addition of the fly ash and the stabilizing agent has a strong accelerating effect on the solidification of the arsenic-containing sludge compared with 20 MPa in the literature; the leaching concentrations of arsenic ions are respectively 3.011 mg/L, 2.787 mg/L and 1.966mg/L, and it can be seen that the leaching toxicity of arsenic is continuously reduced along with the prolonging of time, and the leaching toxicity is less than 5mg/L, which meets the national standard.
Claims (5)
1. A method for targeting arsenic fixation of a fly ash synergistic stabilization medicament is characterized by comprising the following specific steps:
(1) adding portland cement and fly ash into arsenic-containing sludge, and uniformly mixing to obtain a mixture A;
(2) adding a stabilizing agent into the mixture A obtained in the step (1) and uniformly mixing to obtain a mixture B;
(3) under the stirring condition, adding the mixture B in the step (2) into water, uniformly mixing to obtain cement paste, and carrying out aging treatment on the cement paste for 40-60 min;
(4) and (4) pouring the cement paste subjected to the aging treatment in the step (3) into a mould for forming, and naturally curing the formed block for 7-28 days after demoulding to obtain the harmless cured block.
2. The method for targeting arsenic fixation of the fly ash synergistic stabilization medicament according to claim 1, which is characterized in that: the mass ratio of the portland cement, the fly ash and the arsenic-containing sludge in the step (1) is (1:1:2) - (2:2: 3).
3. The method for targeting arsenic fixation of the fly ash synergistic stabilization medicament according to claim 1, which is characterized in that: the arsenic content of the arsenic-containing sludge in the step (1) is 105-136 mg/L.
4. The method for targeting arsenic fixation of the fly ash synergistic stabilization medicament according to claim 1, which is characterized in that: the stabilizing agent in the step (2) is CaO and SiO2MgO and Al2O3Wherein the CaO concentration in the stabilizing agent is 4-5 mg/L, SiO23-4 mg/L, MgO concentration of 1-1.2 mg/L and Al2O3The concentration is 1.2-1.4 mg/L, and the liquid-solid ratio mL of the stabilizing agent to the mixture B is (0.1-0.3): 1.
5. The method for targeting arsenic fixation of the fly ash synergistic stabilization medicament according to claim 1, which is characterized in that: and (3) aging at 40-50 ℃.
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| KR20010007796A (en) * | 2000-09-19 | 2001-02-05 | 최용석 | Solidity material for reapplication of waste |
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Application publication date: 20200228 |