WO2018032810A1 - Matériau composite de traitement, conditionnement et remédiation de sédiments contaminés de rivière ou de lac, et son procédé de fabrication - Google Patents

Matériau composite de traitement, conditionnement et remédiation de sédiments contaminés de rivière ou de lac, et son procédé de fabrication Download PDF

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WO2018032810A1
WO2018032810A1 PCT/CN2017/083620 CN2017083620W WO2018032810A1 WO 2018032810 A1 WO2018032810 A1 WO 2018032810A1 CN 2017083620 W CN2017083620 W CN 2017083620W WO 2018032810 A1 WO2018032810 A1 WO 2018032810A1
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Prior art keywords
conditioning
composite material
sediment
active
river
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PCT/CN2017/083620
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English (en)
Chinese (zh)
Inventor
王民浩
陈士强
翟德勤
刘黎慧
赵新民
王冠东
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中电建水环境治理技术有限公司
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Publication of WO2018032810A1 publication Critical patent/WO2018032810A1/fr

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    • 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
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
    • 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
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
    • C02F11/145—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances using calcium compounds
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • the invention belongs to the technical field of sediment treatment, and particularly relates to a composite material for conditioning and tempering of river and lake pollution sediment treatment and a preparation method thereof.
  • Sediment is an important part of the muddy water environment, a basic factor in the existence and development of social and economic systems, and plays a vital role in supporting the regional economic development. Due to the accumulation of history and the rapid development of recent economic construction, more than 90% of the cities in China have increasingly severe muddy water problems, mainly due to severe siltation of urban rivers, shortage of water resources, excessive water pollution, and disruption of water ecological balance. Wait. The increasingly serious problem of muddy water environment has caused the continuous development of cities to be seriously hindered, and the living environment is increasingly threatened.
  • the object of the present invention is to provide a river and lake pollution sludge treatment conditioning and tempering composite material, aiming at solving the problem that the existing curing agent curing effect is not good, and can not effectively reduce the concentration of organic matter and heavy metals in the sediment. .
  • Another object of the present invention is to provide an application of conditioning and tempering composite materials for polluting sediments in rivers and lakes in the field of conditioning contaminated sediments.
  • the present invention is achieved by a river and lake pollution sludge treatment conditioning and tempering composite material, and the total mass of the composite material is 100%, including the following components in the following mass percentages:
  • Trisodium thiocyanate salt 0.1-1.0 ⁇ 3 ⁇ 4.
  • the present invention provides a river and lake pollution sediment treatment conditioning and tempering composite material, which significantly reduces the heavy metal content, organic pollutants and microbial content in the sediment, so that the concentration of the mud cake leaching liquid is far lower than the GB. 5085.3-2007 Hazardous Waste Identification Standard Leaching Toxicity Identification Standard.
  • the composite material can also disperse and destroy the flocculent and agglomerates in the mud, improve the structural and hydrological characteristics of the mud, accelerate the separation speed of the mud water, and increase the mechanical strength of the sediment solids, so that it can be built. Recycling, backfilling, brick making or production of ceramsite.
  • the invention provides a river and lake flu pollution sediment treatment conditioning and tempering composite material, which has wide application range and can be used for various types of sediments which are polluted. Advantageous effects of the invention
  • Embodiments of the present invention provide a river and lake flu pollution sediment treatment conditioning and tempering composite material, and the total mass of the composite material is 100%, including the following components in the following mass percentages:
  • Trisodium thiocyanate salt 0.1-1.0 ⁇ 3 ⁇ 4.
  • the nanometer-modified cementitious material is used as a main component of the conditioning and tempering composite material of the river and lake pollution sediment, and on the one hand, The particles are reacted, cemented to form minute solidified particles such as ettringite, the strength of the mud cake after dewatering treatment is increased, and the mud water separation efficiency is effectively improved; on the other hand, the nanometer modified cementitious material can be combined with the sediment The heavy metal forms a micro-envelope that is completely encapsulated and passivated into the mud-solidified body.
  • the content of the nanometer-modified cementitious material may not be too low or too high, and if the content of the nanometer-modified cementitious material is too low, the above technical effects cannot be fully realized; Nano-micron modification If the content of the gelling material is too high, the content of other components is relatively lowered, and the respective sexual reproduction cannot be effectively exerted, so that the overall effect is lowered.
  • the mass of the nanometer modified cementitious material is 52-78.7%, based on 100% of the total mass of the conditioning and tempering composite material treated by the river lake.
  • the nanometer-modified cementitious material may have a mass percentage of 52%, 55%, 60%, 65%, 7 0 ⁇ 3 ⁇ 4, 75%, 78.7%, and the like.
  • the nanometer modified gelling material is prepared by the following method:
  • the nano-silica is mixed with a nano-silica by a mass ratio of 1: 0.03-0.06: 0.01-0.04, and a nano-sized modified cementitious material is obtained by grinding.
  • each raw material is weighed according to the content of the above components, and the active Si0 2
  • Active A1 2 0 3 , active CaO, active Fe 2 O 3 , active Na 2 0, and active MgO are essential components for preparing the nanometer-modified cementitious material, and in order to provide photocatalytic oxidation of pollutants, It is preferred to add active Ti0 2 to the above raw materials to enhance the effect of photocatalytic oxidation of contaminants.
  • the content of each raw material component is as described above, and will not be described herein.
  • step (2) the above components are mixed and then sintered.
  • a chemical reaction occurs between the active SiO 2 , the active A 1 2 0 3 , the active CaO, the active Fe 2 O 3 , the active Na 2 0, and the active MgO to form a chemically stable tricalcium silicate, silicon.
  • Active substances such as dicalcium acid.
  • the temperature of the sintering treatment is 1000-1450 ° C, and the calcination time is 20-45 min.
  • the reaction between the substances may not be effectively promoted, or the reaction may not obtain tricalcium silicate, dicalcium silicate, dicalcium aluminate, tricalcium aluminate, iron.
  • the active material such as tetracalcium aluminate or the component of the obtained active material is unstable, and the above properties of the nano-nano modified cementitious material cannot be achieved.
  • the sintered product is mixed with the semi-aqueous CaSO 4 and the nano-silica to obtain a nano-micron-modified cementitious material.
  • the mass ratio of the sintered body to the semi-aqueous CaSO 4 and nano-silica is 1: 0.03-0.06: 0.01-0.04, so that the obtained nano-nano modified cementitious material has a coagulation effect and strength.
  • the content of the semi-aqueous CaSO 4 is too high, the inter-turn and strength of the gelled material may be affected.
  • the nano-nano modified cementitious material has a ⁇ 95 ⁇ 15 ⁇ .
  • the nanometer-modified cementitious material of the preferred particle size can be well dispersed in the sediment particles to act efficiently
  • the polymeric aluminum ferric silicate has an effective content of >36% and an ionicity of greater than 50%.
  • the effective content of the polymeric aluminum ferric silicate is fully ensured; on the other hand, the solubility of the polymeric aluminum aluminum silicate in the sediment mixture can be effectively ensured, thereby exerting its sexuality.
  • the polymeric aluminum silicate can be selected from light yellow flakes or powdered solids.
  • the zeolite powder is natural clinoptilolite powder, and the natural clinoptilolite powder has good adsorption performance to organic pollutants, and may also support Ti0 2 in the nanometer-modified cementitious material. Play the role of photocatalytic oxidation of pollutants.
  • the natural clinoptilolite powder has a fineness of 200-300 mesh, and the preferred natural clinoptilolite powder has a particle size ranging from a boundary between the sand and the mud particle size in the sediment, thereby It is better to disperse in the sediment, adsorb the contaminants in the sediment, and form a large particle precipitate to enter the mud faster.
  • the sodium silicate is a water-soluble salt, that is, a water-soluble sodium silicate.
  • the polymeric aluminum ferrite, the zeolite powder, the sodium silicate, and the like act synergistically to condition and temper the sediment.
  • the polymeric aluminum ferric silicate, the zeolite powder, and the sodium silicate cooperate to destroy the viscosity factor of the floc particles and water in the sediment, and adsorb the colloidal particles which are difficult to precipitate,
  • the negative charge on the surface of the colloid reduces the zeta potential of the colloidal particles, which makes the colloids destabilize, and the colloidal particles attract each other, thereby coagulation and sedimentation, creating an environment in which solid particles and attached moisture are easily separated.
  • the active calcium oxide has a sieve mass fraction of ⁇ 10% after being sieved through a 45 ⁇ square hole, so that it can be sufficiently dispersed in the sediment particles.
  • the active calcium oxide can kill and reduce microorganisms in the contaminated sediment on the one hand; on the other hand, the active calcium oxide and the petroleum pollutants are saponified and degraded to effectively reduce the pollution in the sediment. Oily ingredients.
  • the activated carbon powder is a substance obtained by steam activation of carbon powder, and has high activity. Further preferably, the activated carbon powder has a particle diameter of ⁇ 200 mesh. Since the density of the activated carbon powder is small, if the particle diameter is too small, it is not easily mixed into the contaminated sediment.
  • the trisodium thiocyanate, the activated carbon powder, the zeolite powder, etc. in the examples of the present invention capture heavy metals, organic pollutants, etc. in the contaminated sediment, and then together with other components Heavy metals and organic pollutants precipitated.
  • the trisodium thiocyanate is a polymer salt, and the special polymer spatial structure can be used as a ligand to complex with a heavy metal in the sediment to form a chelate compound.
  • the trisodium thiocyanate salt is less affected by the environment, and the heavy metal ions can be rapidly chelated from the heavy metal complex to form a precipitate in a wide range of pH.
  • the trisodium thiocyanate salt has a polymer structure, and the precipitate can be rapidly precipitated by flocculation.
  • the activated carbon powder, the zeolite powder or the like can effectively adsorb organic contaminants in the sediment, react with the polyaluminum ferric silicate and water to form flocs, and precipitate into the mud.
  • the silicon fine powder is a gray or white powdery solid having a fineness of 800-2500 mesh, thereby facilitating effective dissolution and dispersion thereof in the sediment.
  • the silicon micropowder can cooperate with the nanometer-modified cementitious material and the activated carbon powder to disperse and granulate the sludge floc, and accelerate the contaminated sediment.
  • Fine particles can quickly cure the environmental conditions, and reduce the unfavorable factors of the solidification of the fine particles of the sediment, so that the extremely fine particles can be closely bonded or agglomerated, so that the micro-cure can be performed quickly and effectively.
  • the anhydrite may act as a slow gelling material on the one hand; and another aspect, the anhydrite may act as a sulfate activator to improve the micro-nano modification.
  • the activity of the rice gelling material gradually increases the strength of the sediment.
  • the content of each component of the conditioning and tempering composite material of the river and lake sediments needs to fully meet the above requirements, and the synergistic effect can be effectively achieved, and the heavy metal content in the sediment can be reduced.
  • the content of organic pollutants the role of improving water quality.
  • the natural clinoptilolite powder, the active Ti0 2 , the silicon micropowder, etc. in the composite material capture organic pollutants in the adsorption mud, so that it is precipitated in the mud, and then subjected to pressure filtration dehydration.
  • the organic pollutants in the discharged water are greatly reduced, and the water is regenerated.
  • active Ti0 2 also has photocatalytic oxidation, which can oxidize organic pollutants such as linear aliphatic hydrocarbons and cycloalkanes under the action of ultraviolet rays.
  • the polymer salt such as trisodium thiocyanate has a special polymer space structure, and can be used as a ligand to complex with a heavy metal in the sediment to form a chelate compound. Thereby precipitated; and the trisodium thiocyanate salt is less affected by the environment, and can quickly precipitate heavy metal ions from the heavy metal complex to form a precipitate in a wide pH range.
  • the nano-micron-modified cementitious material is capable of forming a micro-inclusion with the heavy metal in the sediment, so that it is completely encapsulated and passivated into the solidified body.
  • the composite material has a plurality of components that cooperate to reduce the heavy metal content of the contaminated sediment.
  • the composite material can provide an alkaline environment, on the one hand, neutralize the acidic substances in the contaminated sediment, and reduce acidic pollutants, such as hydrogen sulfide; on the other hand, the alkaline environment can The living conditions of the microorganisms, especially the anaerobic bacteria, in the contaminated sediment are changed, the microbial content in the contaminated sediment is reduced, and the anaerobic fermentation reaction is reduced, thereby suppressing the generation of odor.
  • the alkaline conditions formed by the composite material in the embodiment of the invention are also favorable for the precipitation of phosphorus. .
  • the treatment of conditioning and tempering composite materials for river sediments in rivers and lakes can significantly reduce the content of heavy metals, organic pollutants and microorganisms in the sediment, and pollute the mud cake leaching solution.
  • the concentration of the substance is far lower than the standard of the identification of leaching toxicity of the hazardous waste identification standard GB 5085.3-2007.
  • the composite material can also disperse and destroy the flocculent and agglomerates in the mud, improve the structural and hydrological characteristics of the mud, accelerate the separation speed of the mud water, and increase the mechanical strength of the sediment solids, so that it can be built. Recycling, backfilling, brick making or production of ceramsite.
  • the invention provides a river and lake flu pollution sediment treatment conditioning and tempering composite material, which has wide application range and can be used for various types of sediments which are polluted. [0065] Moreover, the embodiment of the invention further provides an application of the above-mentioned river and lake pollution sediment treatment conditioning and quenching and tempering composite material in the field of conditioning contaminated sediment.
  • the application method of the river and lake pollution sediment treatment conditioning and tempering composite material in the field of conditioning contaminated sediment comprises the following steps:
  • the contaminated sediment contains heavy metals and organic substances, and specifically includes mercury, lead, chromium, arsenic, nickel, zinc, copper, and the like.
  • the contaminated sediment is pretreated, so that the mass concentration of the contaminated sediment is 5-20%.
  • the pretreatment essentially adds water to the sediment having a low water content to ensure a certain water content.
  • the contaminated sediment and the composite material for conditioning the sediment are stirred and mixed in a mixer, and the added amount may be determined according to the heavy metal and organic matter content in the contaminated sediment. It is determined that, under the premise of ensuring the effect and saving the cost, the amount of the conditioning and quenching and tempering composite material in the river and lake sediments is 5-20% of the dry weight of the contaminated sediment.
  • step S03 the pulverized mixture after the treatment is mixed into the mud conditioning tank to sufficiently react between the components and the components and the sediment particles.
  • the application of the river and lake pollution sludge treatment conditioning and tempering composite material provided in the embodiment of the invention can effectively reduce the moisture content of the sludge, increase the strength of the sludge, and significantly reduce the sediment.
  • the concentration of organic matter and heavy metals allows the treated sediment to meet the requirements of earthwork filling.
  • a river and lake pollution sediment treatment conditioning conditioning material the total mass of the composite material is 10 0%, including the components of the mass percentage shown in Example 1 in Table 1, wherein the nano-micron-modified cementitious material is obtained by the following method:
  • the obtained sintered product was uniformly mixed with the semi-aqueous CaS0 4 and nano-silica in a ratio of 1:0.05:0.02, and ground to 95 ⁇ 15 ⁇ m to obtain a nano-micron-modified cementitious material.
  • the amount of the conditioning and tempering composite material of the river and lake pollution sedimentation is the dry weight of the contaminated sediment
  • Example 1 of Table 1 after conditioning for 10-30 minutes, it enters the filter press to separate mud and water. Curing completely yields a mud cake.
  • the sediment before conditioning and quenching and tempering shall be tested for pollutants.
  • the test standard is “GB 15618-1995 Soil Environmental Quality Standard”. The test results are shown in Table 2 below.
  • the mud cake leaching solution obtained after conditioning and curing is completely tested.
  • the testing standard is “GB 5085.3-2007 hazardous waste identification standard leaching toxicity identification”, “GB/T50123-1999 geotechnical test method standard”, and the mud after conditioning preparation
  • Table 3 The test results of the cake leaching solution are shown in Table 3, respectively.
  • “undetected” means that the detection limit is lower than the detection method. It can be seen from the results of Tables 2 and 3. Before the conditioning and quenching and tempering, the total concentration of heavy metal pollutants in the sediment is higher, especially copper, exceeding the limit of the third level standard of the Soil Environmental Quality Standard. After conditioning and conditioning, the concentration of mud cake leaching liquid is extremely low, which is lower than that of untreated river channel sediment leaching liquid, and far lower than the “Dangerous Waste Identification Standard Leaching Toxicity Identification”, indicating that heavy metals and organic pollutants are in the conditioning process. It is passivated and stabilized.
  • a river and lake pollution sediment treatment conditioning conditioning material the total mass of the composite material is 100%, including the mass percentage content of the components shown in Table 2 of Table 1, wherein, the preparation method of the nanometer-modified cementitious material is the same as that of the first embodiment.
  • the amount of the treatment and conditioning medium and tempering composite material of the river and lake pollution sediment is the pollution bottom
  • the ratio of the dry weight of the mud is as shown in the second embodiment of Table 1, and after conditioning for 10-30 minutes, it is put into a filter press to separate the mud water and solidify to obtain a mud cake.
  • the sediment before and after conditioning and quenching and tempering shall be tested for pollutants.
  • the test standard is “GB 15618-1995 Soil Environmental Quality Standard”.
  • the total concentration of heavy metal pollutants in the sediment before treatment is high, especially cadmium and nickel, exceeding the soil environment.
  • the standard of the three-level standard of the quality standard, the test results after conditioning and quenching and tempering are shown in Table 4 below.
  • the mud cake leaching solution obtained by curing is tested.
  • the test standard is “GB 5085.3-2007 hazardous waste identification standard leaching toxicity identification” and “GB/T50123-1999 geotechnical test method standard”.
  • the test results are shown in Table 5.
  • not detected means that the detection limit is lower than the detection method. It can be seen from the results in Table 4 and Table 5 that before the conditioning and quenching and tempering, the total concentration of heavy metal pollutants in the sediment is higher, especially nickel, exceeding the limit of the third level standard of the Soil Environmental Quality Standard. After conditioning and conditioning, the concentration of mud cake leaching liquid is extremely low, which is lower than that of untreated river channel sediment leaching liquid, and far lower than the “Dangerous Waste Identification Standard Leaching Toxicity Identification”, indicating that heavy metals and organic pollutants are in the conditioning process. It is passivated and stabilized.
  • the moisture content of the mud cake obtained by pressure filtration decreased from 60.3% to 32.5% (less than 35%), the unconfined compressive strength of 7d was greater than 200 kPa, the improvement was nearly 50 times, and the water resistance was good (7d unconfined resistance)
  • the pressure is measured after the sample is soaked for 24 hours. Therefore, the 7d unconfined compressive strength can indirectly reflect the water resistance).
  • a river and lake pollution sludge treatment conditioning conditioning material the total mass of the composite material is 100%, including the mass percentage content of the components shown in Example 3 of Table 1, Wherein the nanometer modification
  • the preparation method of the gelled material was the same as in Example 1.
  • the soil environmental quality standard, the test results after conditioning and quenching and tempering are shown in Table 6 below.
  • the mud cake leaching solution obtained by curing is tested.
  • the test standard is “GB 5085.3-2007 hazardous waste identification standard leaching toxicity identification”, “GB/T23485-2009 urban sewage treatment plant sewage disposal mixed landfill shale”, test results As shown in Table 7.
  • not detected means that the detection limit is lower than the detection method. It can be seen from the results of Tables 6 and 7 that the heavy metal pollutants, organic pollutants and microbial content of the sediment are higher before conditioning and quenching. After conditioning and conditioning, the concentration of mud cake leaching liquid is extremely low, which is lower than that of untreated river channel sediment leaching liquid, and far lower than the “Dangerous Waste Identification Standard Leaching Toxicity Identification”, indicating that heavy metals and organic pollutants are in the conditioning process. Passivated and stabilized; biological indicators fecal coliform bacteria, worm egg mortality are full Foot standard limit.
  • the mud cake obtained by pressure filtration has a water content of 49.1% (less than 60%) and a transverse shear strength of more than 25 kN/m 2 .
  • the mud cake leaching liquid pollutant is far lower than the hazardous waste identification standard leaching toxicity.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Sludge (AREA)

Abstract

La présente invention décrit un matériau composite destiné au traitement, au conditionnement et à la remédiation de sédiments contaminés de rivière ou de lac. Le matériau composite comprend les constituants suivants, fournis en pourcentages respectifs en masse comme partie de la masse totale du matériau composite : de 52 à 78,7 % d'un matériau de liaison ayant une modification de l'ordre de la nano-échelle ; de 6 à 12 % d'un polysilicate d'aluminium-ferrique ; de 3 à 7 % d'une poudre de zéolite ; de 2 à 8 % d'un oxyde de calcium activé ; de 3 à 6 % d'un gypse anhydre ; de 2 à 6 % de poudre de charbon actif ; de 0,2 à 1 % d'un silicate de sodium ; de 4 à 7 % d'une micro-poudre de silicium ; de 0,1 à 1,0 % d'un sel trisodique d'acide trithiocyanurique. Le matériau composite destiné au traitement, au conditionnement et à la remédiation de sédiments contaminés de rivière ou de lac peut significativement réduire la teneur en métaux lourds, les contaminants organiques et la teneur microbienne d'une boue, peut disperser et dissocier un floculant ou un coagulant dans la boue, améliorer les caractéristiques d'efficacité structurelle et hydrologique, et accélérer la séparation boue-eau.
PCT/CN2017/083620 2016-08-16 2017-05-09 Matériau composite de traitement, conditionnement et remédiation de sédiments contaminés de rivière ou de lac, et son procédé de fabrication WO2018032810A1 (fr)

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CN115771991A (zh) * 2022-12-12 2023-03-10 安徽省通源环境节能股份有限公司 一种聚合硅酸铝铁污泥调理剂及其制备方法

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CN106277858B (zh) * 2016-08-16 2018-03-16 中电建水环境治理技术有限公司 河湖泊涌污染底泥处理纳微米改性胶凝材料
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