CN105694894A - Preparation method and application of hexavalent chromium contaminated soil conditioner - Google Patents
Preparation method and application of hexavalent chromium contaminated soil conditioner Download PDFInfo
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- CN105694894A CN105694894A CN201610154106.6A CN201610154106A CN105694894A CN 105694894 A CN105694894 A CN 105694894A CN 201610154106 A CN201610154106 A CN 201610154106A CN 105694894 A CN105694894 A CN 105694894A
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003516 soil conditioner Substances 0.000 title claims description 4
- 239000002689 soil Substances 0.000 claims abstract description 97
- 239000003814 drug Substances 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000011651 chromium Substances 0.000 claims abstract description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000006872 improvement Effects 0.000 claims abstract description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000010881 fly ash Substances 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 10
- 235000012255 calcium oxide Nutrition 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 239000002893 slag Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000002910 solid waste Substances 0.000 claims description 4
- 238000002798 spectrophotometry method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000002920 hazardous waste Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- -1 gangue Substances 0.000 claims 2
- 239000005696 Diammonium phosphate Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 abstract description 10
- 238000005067 remediation Methods 0.000 abstract description 9
- 231100000419 toxicity Toxicity 0.000 abstract description 8
- 230000001988 toxicity Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 17
- 239000003245 coal Substances 0.000 description 8
- 150000001845 chromium compounds Chemical class 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002364 soil amendment Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明属于土壤修复领域，提供了一种六价铬污染土壤改良剂的制备方法及应用，所述的改良剂由1#药剂与2#药剂组成。所述的改良剂能够高效的将土壤中的六价铬还原为毒性低的三价铬，并改善土壤结构，改良后土壤的酸碱性有效的稳定在一定范围内，保证了三价铬在土壤中长期的稳定性，大大降低了环境风险。本发明所述的改良剂制备方法简单，改良后的土壤六价铬浸出毒性低、酸碱范围适宜、稳定周期长，环境效益明显，有利于土壤的进一步开发利用。该改良剂对六价铬污染土壤的化学修复具有重要的应用意义，市场应用前景广阔。The invention belongs to the field of soil remediation, and provides a preparation method and application of a hexavalent chromium-contaminated soil improver. The improver is composed of 1# medicament and 2# medicament. The improver can efficiently reduce the hexavalent chromium in the soil to trivalent chromium with low toxicity, and improve the soil structure. After improvement, the acidity and alkalinity of the soil can be effectively stabilized within a certain range, ensuring that the trivalent chromium The long-term stability in the soil greatly reduces environmental risks. The improving agent of the invention has a simple preparation method, and the improved soil has low leaching toxicity of hexavalent chromium, suitable acid-base range, long stable period, obvious environmental benefits, and is beneficial to further development and utilization of soil. The improver has important application significance for the chemical remediation of hexavalent chromium-contaminated soil, and has broad market application prospects.
Description
技术领域technical field
本发明属于污染土壤修复技术领域，具体涉及一种六价铬污染土壤改良剂的制备方法及应用。The invention belongs to the technical field of contaminated soil remediation, and in particular relates to a preparation method and application of a hexavalent chromium-contaminated soil improver.
背景技术Background technique
含铬化合物都有毒，在所有含铬化合物中，六价铬的毒性最大，其已被列为对人体危害最大的八种化学物质之一，也是美国环保组织公认的129种重点污染物之一。Chromium-containing compounds are toxic. Among all chromium-containing compounds, hexavalent chromium is the most toxic. It has been listed as one of the eight most harmful chemical substances to the human body, and it is also one of the 129 key pollutants recognized by the US Environmental Protection Organization. .
现有六价铬污染土壤治理的方法有很多，主要有化学淋洗法、生物修复法、电修复法、固化/稳定化法、化学还原法等。其中化学淋洗法可实际应用的范围有限，要求化学淋洗剂能够与土壤内的六价铬充分接触并将其洗脱，该法仅适用于砂壤等渗透系数大的土壤，且其淋洗后淋洗剂必须得到妥善处理，避免二次污染。生物修复法包括微生物修复与植物修复两种，微生物修复是指利用微生物在土壤中的生化作用，将土壤中六价铬还原为三价铬，并将三价铬稳定在土壤中，目前微生物修复技术仍需要大量基础性的研究工作；植物修复技术包括植物提取技术、植物固定技术和植物挥发技术，相对于其他技术来讲，植物修复成本低、环境友好，但是其修复周期长，对于工期要求短的工程，难以实现短期内的快速修复，且对污染程度大的土壤存在难以修复的问题。固化/稳定化法是目前修复重金属污染土壤常用的方法，由于六价铬的高毒性及可还原性，在对其进行固化/稳定化之前，通常要首先将六价铬还原为三价铬。因此，化学还原法是一种有效治理六价铬污染土壤的方法。该法通常以亚铁盐等化学还原剂为基本药剂，土壤的修复周期短、效果明显，可以大规模应用。There are many methods for the treatment of hexavalent chromium-contaminated soil, mainly including chemical leaching method, biological remediation method, electrical remediation method, solidification/stabilization method, chemical reduction method, etc. Among them, the scope of practical application of the chemical leaching method is limited, and it is required that the chemical leaching agent can fully contact with the hexavalent chromium in the soil and elute it. This method is only suitable for soil with a large permeability coefficient such as sandy soil, and its leaching After washing, the rinse agent must be properly disposed of to avoid secondary pollution. Bioremediation includes two types of microbial remediation and phytoremediation. Microbial remediation refers to the use of microorganisms in the soil to reduce hexavalent chromium to trivalent chromium and stabilize trivalent chromium in the soil. At present, microbial remediation The technology still needs a lot of basic research work; phytoremediation technology includes plant extraction technology, plant immobilization technology and plant volatilization technology. Short projects make it difficult to achieve rapid restoration in a short period of time, and it is difficult to repair highly polluted soil. The solidification/stabilization method is currently a common method for repairing heavy metal-contaminated soil. Due to the high toxicity and reducibility of hexavalent chromium, it is usually necessary to reduce hexavalent chromium to trivalent chromium before solidification/stabilization. Therefore, the chemical reduction method is an effective method to control hexavalent chromium-contaminated soil. This method usually uses chemical reducing agents such as ferrous salts as the basic agent, and the soil remediation period is short, the effect is obvious, and it can be applied on a large scale.
所发明的土壤改良剂，在还原六价铬的同时，含有的粉煤灰等硅铝酸盐能改善土壤的结构。此外，三价铬在弱碱性土壤中以Cr(OH)3沉淀的形态存在，改良剂能够将还原后土壤的酸碱维持在一定范围内，有利于铬化合物在改良后土壤中的长期稳定存在。The invented soil conditioner, while reducing the hexavalent chromium, contains aluminosilicates such as fly ash which can improve the structure of the soil. In addition, trivalent chromium exists in the form of Cr(OH) 3 precipitates in weakly alkaline soils, and the amendment can maintain the pH of the reduced soil within a certain range, which is conducive to the long-term stability of chromium compounds in the improved soil exist.
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改良剂的制备方法。One of the purposes of the present invention is to provide a preparation method of hexavalent chromium-contaminated soil improver.
本发明的目的之二是将制备的改良剂用于六价铬污染土壤性质的改良，改良后土壤六价铬的浸出毒性显著降低、土壤结构改善，铬化合物的迁移性及可生物利用性降低。The second object of the present invention is to use the prepared improver to improve the properties of hexavalent chromium-contaminated soil. After improvement, the leaching toxicity of hexavalent chromium in soil is significantly reduced, the soil structure is improved, and the mobility and bioavailability of chromium compounds are reduced. .
本发明的目的之三是改良后土壤酸碱性适宜，三价铬化合物以沉淀态的形式长期在土壤中稳定存在，稳定周期长。The third object of the present invention is that after the improvement, the acidity and alkalinity of the soil are suitable, and the trivalent chromium compound exists stably in the soil for a long time in the form of precipitation, and the stability period is long.
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:
1．一种六价铬污染土壤改良剂的制备方法1. A kind of preparation method of hexavalent chromium polluted soil improver
1）六价铬污染土壤的改良剂由1#药剂与2#药剂组成，1#药剂由六价铬还原剂、粉煤灰、煤矸石、矿渣、生石灰以一定质量比混合搅拌均匀而成，密封避光保存；所述的六价铬还原剂，是由硫酸亚铁、氯化亚铁、亚硫酸钠、硫化钠、多硫化钙中的一种或多种化学还原剂的混合物；1) The improvement agent for hexavalent chromium-contaminated soil is composed of 1# agent and 2# agent. 1# agent is made by mixing and stirring hexavalent chromium reducing agent, fly ash, coal gangue, slag and quicklime in a certain mass ratio. Sealed and protected from light; the hexavalent chromium reducing agent is a mixture of one or more chemical reducing agents in ferrous sulfate, ferrous chloride, sodium sulfite, sodium sulfide, calcium polysulfide;
所述的粉煤灰、煤矸石、矿渣、生石灰，粒径均小于1mm；The particle diameter of the fly ash, coal gangue, slag and quicklime is all less than 1mm;
所述的1#药剂，指按照质量比为六价铬还原剂:粉煤灰:煤矸石:矿渣:生石灰=(40~70):(30~60):(6~10):(2~10):(1~5)混合得到的混合物；Described 1# medicament refers to hexavalent chromium reducing agent according to mass ratio: fly ash: coal gangue: slag: quicklime=(40～70):(30～60):(6～10):(2～ 10): the mixture obtained by mixing (1~5);
2）2#药剂指土壤酸碱缓冲药剂，2#药剂是由四种两性磷酸盐所组成的混合物，其组成及质量比为磷酸氢二铵:磷酸二氢铵:磷酸二氢钠:磷酸氢二钠=(5~10):(10~20):(30~50):(30~50)。2) 2# agent refers to soil acid-base buffer agent, 2# agent is a mixture composed of four amphoteric phosphates, its composition and mass ratio are diammonium hydrogen phosphate: ammonium dihydrogen phosphate: sodium dihydrogen phosphate: hydrogen phosphate Disodium=(5~10):(10~20):(30~50):(30~50).
2．改良剂在六价铬污染土壤改良中的应用2. Application of Improver in Hexavalent Chromium Contaminated Soil Improvement
1）污染土壤六价铬浸出量及pH的测定1) Determination of hexavalent chromium leaching amount and pH in polluted soil
浸提液的制备：将质量比为2:1的浓硫酸与浓硝酸的混合液加入去离子水中，调节pH至3.20±0.05；Preparation of extract solution: add a mixture of concentrated sulfuric acid and concentrated nitric acid with a mass ratio of 2:1 into deionized water, and adjust the pH to 3.20±0.05;
将土样破碎、过9.5mm孔径的筛，按照质量比为土壤:浸提液=1:10的比例，翻转振荡18小时，然后采用《固体废物六价铬测定二苯碳酰二肼分光光度法（GBT15555.4-1995）》测定土壤浸出液中六价铬的含量；The soil sample was crushed, passed through a sieve with a pore size of 9.5mm, and the mass ratio was soil:extraction solution=1:10, turned over and oscillated for 18 hours, and then used "Solid Waste Hexavalent Chromium Determination of Diphenylcarbazide Spectrophotometry" Method (GBT15555.4-1995)" Determination of hexavalent chromium content in soil leachate;
按照国家标准《土壤pH的测定（NY/T1377-2007）》的要求测定土壤pH值；Determine the soil pH value in accordance with the requirements of the national standard "Determination of Soil pH (NY/T1377-2007)";
2）铬污染土壤的改良2) Improvement of chromium-contaminated soil
将土壤破碎、过2mm孔径的筛，调节土壤的含水率至40%~80%，根据土壤中六价铬浸出量及pH值，加入8%~20%的1#药剂，搅拌均匀，养护7~30天后，测定土壤的pH值，再根据需要加入5%~30%的2#药剂，继续养护30~60天，改良后土壤六价铬浸出毒性满足《危险废物鉴别标准浸出毒性鉴别（GB5085.3-2007）》六价铬浸出毒性要求，土壤pH在6~9范围内。Crush the soil, pass it through a sieve with a 2mm aperture, adjust the moisture content of the soil to 40%~80%, add 8%~20% of the 1# agent according to the leaching amount of hexavalent chromium in the soil and the pH value, stir evenly, and maintain for 7 After ~30 days, measure the pH value of the soil, and then add 5%~30% of 2# agent according to the need, and continue to maintain for 30~60 days. The leaching toxicity of hexavalent chromium in the improved soil meets the "hazardous waste identification standard .3-2007) "hexavalent chromium leaching toxicity requirements, soil pH in the range of 6~9.
本发明的效果和益处是：Effect and benefit of the present invention are:
（1）所发明的改良剂将污染土壤中的六价铬转化为三价铬，使六价铬浸出毒性减小，有效的降低了铬化合物的毒性及生物可利用性；(1) The invented improver converts hexavalent chromium in the polluted soil into trivalent chromium, reduces the leaching toxicity of hexavalent chromium, and effectively reduces the toxicity and bioavailability of chromium compounds;
（2）粉煤灰、煤矸石等硅铝酸盐为原料的改良剂，可以改变土壤的物理结构，有利于改良后土壤的进一步开发利用；(2) Aluminosilicate improvers such as fly ash and coal gangue as raw materials can change the physical structure of the soil, which is conducive to the further development and utilization of the improved soil;
（3）土壤酸碱缓冲剂的引入能够增加土壤对酸碱的缓冲能力，将土壤酸碱度长期稳定在一定范围内，三价铬长期以沉淀态存在，铬化合物的迁移性低，有利于改良后土壤低毒性环境的长期维持。(3) The introduction of soil acid-base buffers can increase the buffering capacity of the soil against acid-base, and stabilize the soil pH within a certain range for a long time. Trivalent chromium exists in a precipitated state for a long time, and the mobility of chromium compounds is low, which is beneficial to the improvement. Long-term maintenance of soil low toxicity environment.
具体实施方式detailed description
实施例1六价铬污染土壤改良剂的制备The preparation of embodiment 1 hexavalent chromium polluted soil improver
按照质量比六价铬还原剂:粉煤灰:煤矸石:矿渣:生石灰=60:30:6:3:1混合均匀，制得1#药剂，密封保存，其中，粉煤灰、煤矸石、矿渣、生石灰的粒径均小于1mm；According to the mass ratio of hexavalent chromium reductant: fly ash: coal gangue: slag: quicklime=60:30:6:3:1 mix uniformly, make 1# medicament, seal preservation, wherein, fly ash, coal gangue, The particle size of slag and quicklime is less than 1mm;
按照质量比为磷酸氢二铵:磷酸二氢铵:磷酸二氢钠:磷酸氢二钠=8:15:40:37混合均匀，制得2#药剂。According to the mass ratio of diammonium hydrogen phosphate: ammonium dihydrogen phosphate: sodium dihydrogen phosphate: disodium hydrogen phosphate=8:15:40:37 and mix evenly to prepare 2# medicament.
实施例2六价铬污染土壤改良剂的制备The preparation of embodiment 2 hexavalent chromium polluted soil improver
按照质量比六价铬还原剂:粉煤灰:煤矸石:矿渣:生石灰=40:40:8:8:4混合均匀，制得1#药剂，密封保存，其中，粉煤灰、煤矸石、矿渣、生石灰的粒径均小于1mm；According to the mass ratio of hexavalent chromium reductant: fly ash: coal gangue: slag: quicklime=40:40:8:8:4 mix uniformly, make 1# medicament, seal preservation, wherein, fly ash, coal gangue, The particle size of slag and quicklime is less than 1mm;
按照质量比为磷酸氢二铵:磷酸二氢铵:磷酸二氢钠:磷酸氢二钠=10:10:50:30混合均匀，制得2#药剂。According to the mass ratio of diammonium hydrogen phosphate: ammonium dihydrogen phosphate: sodium dihydrogen phosphate: disodium hydrogen phosphate=10:10:50:30 and mix evenly to prepare 2# medicament.
实施例3改良剂在六价铬污染土壤改良剂中的应用Application of embodiment 3 amendments in hexavalent chromium-contaminated soil amendments
1）污染土壤六价铬浸出量及pH的测定1) Determination of hexavalent chromium leaching amount and pH in polluted soil
浸提液的制备：将质量比为2:1的浓硫酸与浓硝酸的混合液加入去离子水中，调节pH至3.20±0.05；Preparation of extract solution: add a mixture of concentrated sulfuric acid and concentrated nitric acid with a mass ratio of 2:1 into deionized water, and adjust the pH to 3.20±0.05;
将土样破碎、过9.5mm孔径的筛，按照质量比为土壤:浸提液=1:10的比例，翻转振荡18小时，然后采用《固体废物六价铬测定二苯碳酰二肼分光光度法（GBT15555.4-1995）》测定土壤浸出液中六价铬的含量；The soil sample was crushed, passed through a sieve with a pore size of 9.5mm, and the mass ratio was soil:extraction solution=1:10, turned over and oscillated for 18 hours, and then used "Solid Waste Hexavalent Chromium Determination of Diphenylcarbazide Spectrophotometry" Method (GBT15555.4-1995)" Determination of hexavalent chromium content in soil leachate;
按照国家标准《土壤pH的测定（NY/T1377-2007）》的要求测定土壤pH值；Determine the soil pH value in accordance with the requirements of the national standard "Determination of Soil pH (NY/T1377-2007)";
2）铬污染土壤的改良2) Improvement of chromium-contaminated soil
将土壤破碎、过2mm孔径的筛，调节土壤的含水率至60%，根据土壤中六价铬浸出量及pH值，加入10%的1#药剂，搅拌均匀，养护30天后，测定土壤的pH值，再根据需要加入10%的2#药剂，继续养护40天，检测改良后土壤六价铬浸出毒性及pH满足要求；Crush the soil, pass it through a sieve with a 2mm aperture, adjust the moisture content of the soil to 60%, add 10% of the 1# agent according to the leaching amount of hexavalent chromium in the soil and the pH value, stir evenly, and measure the pH of the soil after 30 days of maintenance value, and then add 10% of 2# agent according to the need, continue to maintain for 40 days, and test the soil hexavalent chromium leaching toxicity and pH to meet the requirements after the improvement;
所述的1#药剂，为实施例1或实施例2所制备的1#药剂；The 1# medicament is the 1# medicament prepared in Example 1 or Example 2;
所述的2#药剂，为实施例1或实施例2所制备的2#药剂。The 2# medicament is the 2# medicament prepared in Example 1 or Example 2.
实施例4改良剂在六价铬污染土壤改良剂中的应用Application of embodiment 4 improver in hexavalent chromium polluted soil improver
1）污染土壤六价铬浸出量及pH的测定1) Determination of hexavalent chromium leaching amount and pH in polluted soil
浸提液的制备：将质量比为2:1的浓硫酸与浓硝酸的混合液加入去离子水中，调节pH至3.20±0.05；Preparation of extract solution: add a mixture of concentrated sulfuric acid and concentrated nitric acid with a mass ratio of 2:1 into deionized water, and adjust the pH to 3.20±0.05;
将土样破碎、过9.5mm孔径的筛，按照质量比为土壤:浸提液=1:10的比例，翻转振荡18小时，然后采用《固体废物六价铬测定二苯碳酰二肼分光光度法（GBT15555.4-1995）》测定土壤浸出液中六价铬的含量；The soil sample was crushed, passed through a sieve with a pore size of 9.5mm, and the mass ratio was soil:extraction solution=1:10, turned over and oscillated for 18 hours, and then used "Solid Waste Hexavalent Chromium Determination of Diphenylcarbazide Spectrophotometry" Method (GBT15555.4-1995)" Determination of hexavalent chromium content in soil leachate;
按照国家标准《土壤pH的测定（NY/T1377-2007）》的要求测定土壤pH值；Determine the soil pH value in accordance with the requirements of the national standard "Determination of Soil pH (NY/T1377-2007)";
2）铬污染土壤的改良2) Improvement of chromium-contaminated soil
将土壤破碎、过2mm孔径的筛，调节土壤的含水率至50%，根据土壤中六价铬浸出量及pH值，加入20%的1#药剂，搅拌均匀，养护30天后，测定土壤的pH值，再根据需要加入5%的2#药剂，继续养护60天，检测改良后土壤六价铬浸出毒性及pH满足要求；Crush the soil, pass it through a sieve with a pore size of 2 mm, adjust the moisture content of the soil to 50%, add 20% of the 1# agent according to the leaching amount of hexavalent chromium in the soil and the pH value, stir evenly, and measure the pH of the soil after 30 days of curing value, and then add 5% of 2# agent according to the need, and continue to maintain for 60 days. After testing the improved soil hexavalent chromium leaching toxicity and pH meet the requirements;
所述的1#药剂，为实施例1或实施例2所制备的1#药剂；The 1# medicament is the 1# medicament prepared in Example 1 or Example 2;
所述的2#药剂，为实施例1或实施例2所制备的2#药剂。The 2# medicament is the 2# medicament prepared in Example 1 or Example 2.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106583436A (en) * | 2016-12-16 | 2017-04-26 | 亿利首建生态科技有限公司 | Leaching method for remediating hexavalent chromium contaminated soil |
| CN106734169A (en) * | 2016-12-28 | 2017-05-31 | 广西博世科环保科技股份有限公司 | The processing method and processing equipment of repairing hexavalent chromium polluted soil |
| CN106984644A (en) * | 2017-05-10 | 2017-07-28 | 青岛科技大学 | The preparation of calcium polysulfide renovation agent and its application in pollution law |
| CN107486468A (en) * | 2017-08-15 | 2017-12-19 | 北京高能时代环境技术股份有限公司 | One kind is used for hexavalent chromium polluted soil heterotopic repairing method of microorganism |
| CN108276228A (en) * | 2018-01-16 | 2018-07-13 | 航天凯天环保科技股份有限公司 | One kind being used for the fertilizer and preparation method thereof of Cr (VI) contaminated soil remediations and improvement |
| CN108356069A (en) * | 2018-01-30 | 2018-08-03 | 上海岩土工程勘察设计研究院有限公司 | Polluted Soil stir in situ uniformity computational discrimination method |
| CN108726823A (en) * | 2017-12-19 | 2018-11-02 | 上海傲江生态环境科技有限公司 | The method that greasy filth stabilizes solidification medicament and repairs Heavy Metal Pollution in Sediments soil |
| CN109226239A (en) * | 2018-10-14 | 2019-01-18 | 中国计量大学 | A method of chromium-polluted soil is repaired using alkaline coal ash |
| 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 |
| CN116174464A (en) * | 2023-03-06 | 2023-05-30 | 核工业北京化工冶金研究院 | Secondary restoration stable solidification method for 'yellowing' chromium-polluted soil |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228901A (en) * | 2010-06-11 | 2011-11-02 | 中国地质大学（北京） | Treatment method of chromium-polluted soil |
| CN103920701A (en) * | 2014-04-24 | 2014-07-16 | 杭州大地环保工程有限公司 | Method for restoring chromium-polluted soil |
| CN104232100A (en) * | 2014-08-19 | 2014-12-24 | 安徽红太阳新材料有限公司 | Chromium-polluted soil modifier |
| CN104312591A (en) * | 2014-10-13 | 2015-01-28 | 贵州美瑞特环保科技有限公司 | Stabilized curing agent for heavy metal contaminated soil or solid waste treatment and treatment method |
| CN104498044A (en) * | 2014-11-28 | 2015-04-08 | 浙江卓锦工程技术有限公司 | Hexavalent chromium-contaminated soil remediation agent and preparation method thereof |
| CN104841693A (en) * | 2015-05-29 | 2015-08-19 | 北京大学 | Hexavalent chromium contaminated soil in-situ remediation method |
| CN105013810A (en) * | 2014-04-16 | 2015-11-04 | 永清环保股份有限公司 | Chromium-contaminated soil remediation medicament and remediation method |
| CN105238409A (en) * | 2015-11-04 | 2016-01-13 | 北京高能时代环境技术股份有限公司 | Linkage stabilizing agent for repairing heavy metal contaminated soil and repairing method |
-
2016
- 2016-03-18 CN CN201610154106.6A patent/CN105694894A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228901A (en) * | 2010-06-11 | 2011-11-02 | 中国地质大学（北京） | Treatment method of chromium-polluted soil |
| CN105013810A (en) * | 2014-04-16 | 2015-11-04 | 永清环保股份有限公司 | Chromium-contaminated soil remediation medicament and remediation method |
| CN103920701A (en) * | 2014-04-24 | 2014-07-16 | 杭州大地环保工程有限公司 | Method for restoring chromium-polluted soil |
| CN104232100A (en) * | 2014-08-19 | 2014-12-24 | 安徽红太阳新材料有限公司 | Chromium-polluted soil modifier |
| CN104312591A (en) * | 2014-10-13 | 2015-01-28 | 贵州美瑞特环保科技有限公司 | Stabilized curing agent for heavy metal contaminated soil or solid waste treatment and treatment method |
| CN104498044A (en) * | 2014-11-28 | 2015-04-08 | 浙江卓锦工程技术有限公司 | Hexavalent chromium-contaminated soil remediation agent and preparation method thereof |
| CN104841693A (en) * | 2015-05-29 | 2015-08-19 | 北京大学 | Hexavalent chromium contaminated soil in-situ remediation method |
| CN105238409A (en) * | 2015-11-04 | 2016-01-13 | 北京高能时代环境技术股份有限公司 | Linkage stabilizing agent for repairing heavy metal contaminated soil and repairing method |
Non-Patent Citations (2)
| Title |
|---|
| 尹贞: "几种稳定化药剂修复铬污染土壤的研究", 《环境工程》 * |
| 陈森等: "硫酸亚铁修复六价铬污染土壤实验研究", 《安徽农学通报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106583436A (en) * | 2016-12-16 | 2017-04-26 | 亿利首建生态科技有限公司 | Leaching method for remediating hexavalent chromium contaminated soil |
| CN106734169A (en) * | 2016-12-28 | 2017-05-31 | 广西博世科环保科技股份有限公司 | The processing method and processing equipment of repairing hexavalent chromium polluted soil |
| CN106984644A (en) * | 2017-05-10 | 2017-07-28 | 青岛科技大学 | The preparation of calcium polysulfide renovation agent and its application in pollution law |
| CN107486468A (en) * | 2017-08-15 | 2017-12-19 | 北京高能时代环境技术股份有限公司 | One kind is used for hexavalent chromium polluted soil heterotopic repairing method of microorganism |
| CN108726823A (en) * | 2017-12-19 | 2018-11-02 | 上海傲江生态环境科技有限公司 | The method that greasy filth stabilizes solidification medicament and repairs Heavy Metal Pollution in Sediments soil |
| CN108276228A (en) * | 2018-01-16 | 2018-07-13 | 航天凯天环保科技股份有限公司 | One kind being used for the fertilizer and preparation method thereof of Cr (VI) contaminated soil remediations and improvement |
| CN108356069A (en) * | 2018-01-30 | 2018-08-03 | 上海岩土工程勘察设计研究院有限公司 | Polluted Soil stir in situ uniformity computational discrimination method |
| CN109226239A (en) * | 2018-10-14 | 2019-01-18 | 中国计量大学 | A method of chromium-polluted soil is repaired using alkaline coal ash |
| 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 |
| CN116174464A (en) * | 2023-03-06 | 2023-05-30 | 核工业北京化工冶金研究院 | Secondary restoration stable solidification method for 'yellowing' chromium-polluted soil |
| CN116174464B (en) * | 2023-03-06 | 2024-05-14 | 核工业北京化工冶金研究院 | Secondary restoration stable solidification method for 'yellowing' chromium-polluted soil |
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