CN105665436B - A kind of method of resource of hexavalent chromium polluted soil - Google Patents
A kind of method of resource of hexavalent chromium polluted soil Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims abstract description 80
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000011449 brick Substances 0.000 claims abstract description 28
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 239000011651 chromium Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 238000002386 leaching Methods 0.000 claims abstract description 7
- 239000004035 construction material Substances 0.000 claims abstract 2
- 150000002500 ions Chemical class 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000012190 activator Substances 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 8
- 238000012423 maintenance Methods 0.000 claims description 8
- 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 7
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 235000012255 calcium oxide Nutrition 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 10
- 239000003245 coal Substances 0.000 description 8
- 238000009415 formwork Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000004566 building material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012954 risk control Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
Abstract
Description
技术领域technical field
本发明涉及污染土壤资源化技术，尤其涉及一种六价铬污染土壤的资源化方法，将污染土壤用于制砖，作为建筑材料资源化使用。The present invention relates to the recycling technology of polluted soil, in particular to a resource recycling method of hexavalent chromium contaminated soil. The contaminated soil is used for making bricks and used as a resource recycling of building materials.
背景技术Background technique
随着工业的发展和资源的利用，我国的土壤正遭受着越来越严重的污染问题。铬化合物的污染主要来自于铬盐生产、电镀、制革和制药等行业排放的三废物质，这些铬大多以六价铬的形式存在，具有强毒性，进入土壤及地下水后对人体健康造成严重危害。根据相关统计数据，我国目前仍存在遗留铬渣堆放场地40多处，绝大部分处于弃置状态，无人治理；在我国1000多家镀铬厂中，有部分厂址出现了土壤和地下水的严重污染问题。这些存在严重铬污染的场地，急需风险管控和修复治理，以彻底解决铬的污染问题。With the development of industry and the utilization of resources, the soil of our country is suffering from more and more serious pollution problems. The pollution of chromium compounds mainly comes from the three wastes discharged from chromium salt production, electroplating, tanning and pharmaceutical industries. Most of these chromium exists in the form of hexavalent chromium, which is highly toxic and will cause serious harm to human health after entering the soil and groundwater. . According to relevant statistical data, there are still more than 40 places where chromium slag is left behind in my country, most of which are abandoned and left untreated; among the more than 1,000 chromium plating factories in my country, some of them have serious pollution problems of soil and groundwater . These sites with serious chromium pollution urgently need risk control and restoration treatment to completely solve the problem of chromium pollution.
发明内容Contents of the invention
本发明的目的之一是提供一种六价铬污染土壤资源化的方法。One of the objectives of the present invention is to provide a method for recycling hexavalent chromium-contaminated soil.
本发明的目的之二是将处理后的污染土壤作为制砖原料使用。The second object of the present invention is to use the treated polluted soil as a raw material for making bricks.
本发明的目的之三是将六价铬污染土壤为原料制得的砖块作为建筑材料使用。The third object of the present invention is to use the bricks made from hexavalent chromium-contaminated soil as building materials.
本发明是通过如下的技术方案实施的，具体按照以下步骤实施：The present invention is implemented through the following technical solutions, specifically implemented according to the following steps:
一种六价铬污染土壤的资源化方法A kind of resource recovery method of hexavalent chromium polluted soil
（1）土壤中六价铬的还原：将污染土壤破碎，过100目筛，加水调节土壤含水率至40%-60%，根据土壤中六价铬含量，加入一定量的硫酸亚铁，养护7天，要求六价铬还原率大于95%；(1) Reduction of hexavalent chromium in soil: crush the contaminated soil, pass through a 100-mesh sieve, add water to adjust the soil moisture content to 40%-60%, add a certain amount of ferrous sulfate according to the content of hexavalent chromium in the soil, and maintain 7 days, the reduction rate of hexavalent chromium is required to be greater than 95%;
（2）土壤与资源化药剂的混合：将还原剂处理后的土壤与资源化药剂、激活剂按照质量比(10-40):(20-50):(4-10)充分搅拌混匀，得到土壤混合物；(2) Mixing of soil and resource-based chemicals: fully stir and mix the soil treated with reducing agent with resource-based chemicals and activators according to the mass ratio (10-40):(20-50):(4-10), get the soil mixture;
（3）砖块制备及养护：将土壤混合物加入制砖模具中，加水调节含水率至30%-70%，搅拌混匀、振实，然后将其置于养护箱中，在温度20-50℃、相对湿度40-90%的条件下养护24小时后拆模，继续在该条件下养护7-30天，养护后得到的砖块，其抗压强度大于7.5MPa，六价铬浸出浓度小于0.5mg/L，砖块作为建筑材料资源化使用；(3) Brick preparation and maintenance: Add the soil mixture into the brick mold, add water to adjust the moisture content to 30%-70%, stir and vibrate, then put it in the curing box, at a temperature of 20-50 After curing for 24 hours under the conditions of ℃ and relative humidity of 40-90%, the formwork is removed, and the curing is continued for 7-30 days under this condition. 0.5mg/L, bricks are used as building materials;
所述的资源化药剂，指按照质量比偏高岭土:煤矸石:沸石=(60-80):(20-40):(10-20)混匀得到的混合物其中，偏高领土、煤矸石、沸石均过100目筛；The resource-based agent refers to the mixture obtained by mixing metakaolin: coal gangue: zeolite=(60-80):(20-40):(10-20) by mass ratio. The zeolite has passed through a 100 mesh sieve;
所述的激活剂，指按照质量比水玻璃:苛性钠:生石灰=(60-80):(8-15):(1-5)混匀得到的混合物。The activator refers to the mixture obtained by mixing uniformly according to the mass ratio of water glass: caustic soda: quicklime=(60-80):(8-15):(1-5).
本发明的效果和益处是：Effect and benefit of the present invention are:
（1）环境效益好。经还原剂作用后，土壤中大部分六价铬被还原为三价铬，铬化合物的迁移性明显降低；以偏高岭土为主要成分的资源化药剂在制砖过程中能够有效固定铬化合物，制得的砖块六价铬浸出毒性小于0.5 mg/L；(1) Good environmental benefits. After the action of the reducing agent, most of the hexavalent chromium in the soil is reduced to trivalent chromium, and the mobility of chromium compounds is significantly reduced; the resource-based agent with metakaolin as the main component can effectively fix chromium compounds in the brick-making process, making The hexavalent chromium leaching toxicity of the obtained bricks is less than 0.5 mg/L;
（2）资源化方法简单。通过将土壤与资源化药剂混匀、制模、养护过程，即可得到砖块，方法简单；(2) The resource utilization method is simple. Bricks can be obtained through the process of mixing soil and resourceful agents, making molds and curing, and the method is simple;
（3）经济效益好。将污染土壤用于制砖，实现了污染土壤的资源化利用，降低了制砖成本，经济效益明显，并解决了目前修复后土壤不方便处置的问题。(3) Good economic benefits. The use of polluted soil for brick making realizes the resource utilization of polluted soil, reduces the cost of brick making, has obvious economic benefits, and solves the problem of inconvenient disposal of soil after restoration.
具体实施方式Detailed ways
实施例1 六价铬污染土壤的资源化Example 1 Recycling of Hexavalent Chromium Contaminated Soil
（1）土壤中六价铬的还原：将污染土壤破碎，过100目筛，加水调节土壤含水率至40%，根据土壤中六价铬含量，加入一定量的硫酸亚铁，养护7天；(1) Reduction of hexavalent chromium in soil: crush the contaminated soil, pass through a 100-mesh sieve, add water to adjust the soil moisture content to 40%, add a certain amount of ferrous sulfate according to the content of hexavalent chromium in the soil, and maintain for 7 days;
（2）土壤与资源化药剂的混合：将还原剂处理后的土壤与资源化药剂、激活剂按照质量比10:30:4充分搅拌混匀，得到土壤混合物；(2) Mixing of soil and resource-based chemicals: fully stir and mix the soil treated with reducing agent, resource-based chemicals, and activators at a mass ratio of 10:30:4 to obtain a soil mixture;
（3）砖块制备及养护：将土壤混合物加入制砖模具中，加水调节含水率至40%，搅拌混匀、振实，然后将其置于养护箱中，在温度20℃、相对湿度50%的条件下养护24小时后拆模，继续在该条件下养护10天，测试养护后砖块的抗压强度及六价铬浸出浓度；(3) Brick preparation and maintenance: Add the soil mixture into the brick mold, add water to adjust the moisture content to 40%, stir and shake, and then place it in a curing box at a temperature of 20 ° C and a relative humidity of 50 % under the condition of curing for 24 hours, remove the formwork, continue to maintain under this condition for 10 days, test the compressive strength of the bricks after curing and the leaching concentration of hexavalent chromium;
所述的资源化药剂，指按照质量比偏高岭土:煤矸石:沸石=60:30:10混匀得到的混合物；The resource-based medicament refers to the mixture obtained by mixing metakaolin in mass ratio: coal gangue: zeolite=60:30:10;
所述的激活剂，指按照质量比水玻璃:苛性钠:生石灰=60:8:2混匀得到的混合物。Described activator refers to the mixture obtained by mixing according to the mass ratio of water glass: caustic soda: quicklime=60:8:2.
实施例2 六价铬污染土壤的资源化Example 2 Recycling of Hexavalent Chromium Contaminated Soil
（1）土壤中六价铬的还原：将污染土壤破碎，过100目筛，加水调节土壤含水率至50%，根据土壤中六价铬含量，加入一定量的硫酸亚铁，养护7天；(1) Reduction of hexavalent chromium in soil: crush the contaminated soil, pass through a 100-mesh sieve, add water to adjust the soil moisture content to 50%, add a certain amount of ferrous sulfate according to the content of hexavalent chromium in the soil, and maintain for 7 days;
（2）土壤与资源化药剂的混合：将还原剂处理后的土壤与资源化药剂、激活剂按照质量比10:30:4充分搅拌混匀，得到土壤混合物；(2) Mixing of soil and resource-based chemicals: fully stir and mix the soil treated with reducing agent, resource-based chemicals, and activators at a mass ratio of 10:30:4 to obtain a soil mixture;
（3）砖块制备及养护：将土壤混合物加入制砖模具中，加水调节含水率至40%，搅拌混匀、振实，然后将其置于养护箱中，在温度40℃、相对湿度70%的条件下养护24小时后拆模，继续在该条件下养护20天，测试养护后砖块的抗压强度及六价铬浸出浓度；(3) Brick preparation and maintenance: Add the soil mixture into the brick mold, add water to adjust the moisture content to 40%, stir and shake, and then place it in a curing box at a temperature of 40°C and a relative humidity of 70%. % under the condition of curing for 24 hours, remove the formwork, continue to maintain under this condition for 20 days, test the compressive strength of the bricks after curing and the concentration of hexavalent chromium leaching;
所述的资源化药剂，指按照质量比偏高岭土:煤矸石:沸石=60:20:10混匀得到的混合物，其中，偏高领土、煤矸石、沸石均过100目筛；The resource-based medicament refers to a mixture obtained by mixing metakaolin: coal gangue: zeolite=60:20:10 by mass, wherein the high-grade soil, coal gangue, and zeolite all pass through a 100-mesh sieve;
所述的激活剂，指按照质量比水玻璃:苛性钠:生石灰=70:10:2混匀得到的混合物。Described activator refers to the mixture obtained by mixing according to the mass ratio of water glass: caustic soda: quicklime=70:10:2.
实施例3 六价铬污染土壤的资源化Example 3 Recycling of Hexavalent Chromium Contaminated Soil
（1）土壤中六价铬的还原：将污染土壤破碎，过100目筛，加水调节土壤含水率至60%，根据土壤中六价铬含量，加入一定量的硫酸亚铁，养护7天；(1) Reduction of hexavalent chromium in soil: crush the contaminated soil, pass through a 100-mesh sieve, add water to adjust the soil moisture content to 60%, add a certain amount of ferrous sulfate according to the content of hexavalent chromium in the soil, and maintain for 7 days;
（2）土壤与资源化药剂的混合：将还原剂处理后的土壤与资源化药剂、激活剂按照质量比10:50:10充分搅拌混匀，得到土壤混合物；(2) Mixing of soil and resource-based chemicals: fully mix the soil treated with the reducing agent with resource-based chemicals and activators at a mass ratio of 10:50:10 to obtain a soil mixture;
（3）砖块制备及养护：将土壤混合物加入制砖模具中，加水调节含水率至60%，搅拌混匀、振实，然后将其置于养护箱中，在温度50℃、相对湿度80%的条件下养护24小时后拆模，继续在该条件下养护30天，测试养护后砖块的抗压强度及六价铬浸出浓度；(3) Brick preparation and maintenance: Add the soil mixture into the brick mold, add water to adjust the moisture content to 60%, stir and shake, and then place it in a curing box at a temperature of 50 ° C and a relative humidity of 80 % of the condition of curing 24 hours after removal of formwork, continue to maintain under this condition for 30 days, test the compressive strength of the bricks after curing and hexavalent chromium leaching concentration;
所述的资源化药剂，指按照质量比偏高岭土:煤矸石:沸石=80:20:10混匀得到的混合物，其中，偏高领土、煤矸石、沸石均过100目筛；The resource-based medicament refers to a mixture obtained by mixing metakaolin: coal gangue: zeolite=80:20:10 by mass, wherein the high-grade soil, coal gangue, and zeolite all pass through a 100-mesh sieve;
所述的激活剂，指按照质量比水玻璃:苛性钠:生石灰=80:10:2混匀得到的混合物。Described activator refers to the mixture obtained by mixing according to the mass ratio of water glass: caustic soda: quicklime=80:10:2.
实施例4 六价铬污染土壤的资源化Example 4 Recycling of Hexavalent Chromium Contaminated Soil
（1）土壤中六价铬的还原：将污染土壤破碎，过100目筛，加水调节土壤含水率至60%，根据土壤中六价铬含量，加入一定量的硫酸亚铁，养护7天；(1) Reduction of hexavalent chromium in soil: crush the contaminated soil, pass through a 100-mesh sieve, add water to adjust the soil moisture content to 60%, add a certain amount of ferrous sulfate according to the content of hexavalent chromium in the soil, and maintain for 7 days;
（2）土壤与资源化药剂的混合：将还原剂处理后的土壤与资源化药剂、激活剂按照质量比10:50:10充分搅拌混匀，得到土壤混合物；(2) Mixing of soil and resource-based chemicals: fully mix the soil treated with the reducing agent with resource-based chemicals and activators at a mass ratio of 10:50:10 to obtain a soil mixture;
（3）砖块制备及养护：将土壤混合物加入制砖模具中，加水调节含水率至70%，搅拌混匀、振实，然后将其置于养护箱中，在温度50℃、相对湿度90%的条件下养护24小时后拆模，继续在该条件下养护30天，测试养护后砖块的抗压强度及六价铬浸出浓度；(3) Preparation and maintenance of bricks: Add the soil mixture into the brick mold, add water to adjust the moisture content to 70%, stir and vibrate, and then place it in a curing box at a temperature of 50°C and a relative humidity of 90%. % of the condition of curing 24 hours after removal of formwork, continue to maintain under this condition for 30 days, test the compressive strength of the bricks after curing and hexavalent chromium leaching concentration;
所述的资源化药剂，指按照质量比偏高岭土:煤矸石:沸石=80:30:10混匀得到的混合物，其中，偏高领土、煤矸石、沸石均过100目筛；The resource-based medicament refers to a mixture obtained by mixing metakaolin: coal gangue: zeolite=80:30:10 by mass, wherein the high-grade soil, coal gangue, and zeolite all pass through a 100-mesh sieve;
所述的激活剂，指按照质量比水玻璃:苛性钠:生石灰=70:10:2混匀得到的混合物。Described activator refers to the mixture obtained by mixing according to the mass ratio of water glass: caustic soda: quicklime=70:10:2.
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| CN107790478A (en) * | 2017-07-28 | 2018-03-13 | 安徽国祯环境修复股份有限公司 | A kind of method that pollution of chromium soil resource utilizes |
| CN108746187B (en) * | 2018-05-25 | 2020-07-31 | 中国科学院沈阳应用生态研究所 | A harmless and resource-based restoration method for chromium-contaminated soil |
| CN109719115A (en) * | 2018-12-15 | 2019-05-07 | 佛山市铁人环保科技有限公司 | A kind of place heavy-metal contaminated soil recycling low cost method of disposal |
| CN111185474A (en) * | 2020-01-16 | 2020-05-22 | 招商局生态环保科技有限公司 | Chromium-contaminated soil in-situ remediation composite reagent and use method thereof |
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