WO2021175156A1 - 反应型固化稳定组合物及其制备方法和应用 - Google Patents

反应型固化稳定组合物及其制备方法和应用 Download PDF

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WO2021175156A1
WO2021175156A1 PCT/CN2021/078042 CN2021078042W WO2021175156A1 WO 2021175156 A1 WO2021175156 A1 WO 2021175156A1 CN 2021078042 W CN2021078042 W CN 2021078042W WO 2021175156 A1 WO2021175156 A1 WO 2021175156A1
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active metal
ball milling
composition
calcium oxide
fly ash
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PCT/CN2021/078042
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English (en)
French (fr)
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刘建国
于书尧
江宇辉
巴黑多拉阿曼角
尚奕萱
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清华大学
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Publication of WO2021175156A1 publication Critical patent/WO2021175156A1/zh

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/20—Agglomeration, binding or encapsulation of solid waste
    • 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
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/08—Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B2101/00—Type of solid waste
    • B09B2101/30—Incineration ashes

Definitions

  • the present invention belongs to the field of environmental protection, and relates to the treatment of waste or pollutants. More specifically, the present invention belongs to the field of fly ash solidification and stabilization pollution control, and specifically relates to a solidification and stabilization component and a preparation method thereof and fixing heavy metals in fly ash A method of detoxification simultaneously with harmful organic compounds.
  • fly ash produced by the flue gas purification system of the domestic waste incineration plant can reach 4.9 million tons per year.
  • domestic waste incineration fly ash has the characteristics of small particles, large porosity, and strong alkalinity. It contains a large amount of heavy metals and persistent organic pollutants, including dioxins, chlorobenzenes, polychlorinated biphenyls, etc., and has high environmental risks , Is managed as a list of hazardous wastes in our country.
  • the commonly used fly ash treatment methods include curing/stabilization treatment.
  • cement is a common curing agent.
  • the commonly used cement is used to cure the combustion fly ash. After the fly ash is mixed into the cement matrix, under certain conditions Under certain physical and chemical effects, the leaching and migration rate of harmful substances in the cement matrix is reduced.
  • Reference 1 discloses a waste incineration fly ash curing agent, which contains 80 to 95 parts of pyrite and 5 to 20 parts of calcium carbonate per 100 parts. The powder is mixed and prepared. The use of the curing agent to treat the waste incineration fly ash can effectively solidify the harmful substances (including heavy metals, arsenic, fluorine, etc.) in the waste incineration fly ash with a short curing age.
  • Reference 2 discloses a fly ash solidified heavy metal chelating agent, which comprises the following parts by weight of raw materials: 20-40 parts of polycarboxylate ammonium salt, 20-30 parts of dimercaptoethylamine hydrochloride, aminomethane vinegar 15-25 parts of acid salt, 10-20 parts of thioacetate, 30-50 parts of water, 5-10 parts of surfactant.
  • the chelating agent has strong chelating ability, good thermal stability and convenient preparation.
  • the treatment method of cement curing or chelating agent stabilization cannot degrade and remove persistent organic pollutants, and because of its strong fat solubility, it is not easy to be fixed by the inorganic mineral structure, and it gradually migrates into the atmosphere during the process of piling up and burying in the landfill. , Groundwater and soil.
  • Reference 3 discloses a preparation method and application of a nano-dispersed mixture.
  • the nano-dispersed mixture prepared from aluminum powder and calcium oxide can be applied to the complex contaminated soil of heavy metals and organics, but there is cold welding in the actual preparation.
  • the technical problem to be solved by the present invention is first to provide a reactive curing and stable composition particularly suitable for fly ash, the composition including active metals and calcium oxide,
  • the composition has an average particle size of 100-300nm, and the active metal is dispersed in the layered calcium oxide as a continuous phase.
  • the composition can improve the resistance to heavy metals in fly ash.
  • Another object of the present invention is to provide a stable and efficient method for preparing the above-mentioned reactive curing stabilizer.
  • the present invention also provides a method for treating fly ash using the above-mentioned reactive curing stabilizer.
  • the present invention first provides a reactive curing and stabilizing composition, the composition comprising an active metal and calcium oxide, the active metal is selected from one or more of aluminum, iron and magnesium,
  • the composition has an average particle diameter of 100 to 300 nm, the active metal is dispersed in layered calcium oxide as a continuous phase, and
  • the average particle size of the active metal is 10 to 120 nm, and the layer thickness of the layered calcium oxide is 50 to 150 nm.
  • composition according to [1] in terms of the total mass of the composition, the content of the active metal is 25%-40%, and the content of the calcium oxide is 60%-75%.
  • composition according to [1] or [2], in the active metal, the content of aluminum is 70% or more based on the total mass of the active metal.
  • the hydrophobic organic group includes a substituted or unsubstituted hydrocarbyl group.
  • the present invention provides a method for preparing the composition according to any one of [1] to [4], the method comprising: ball milling active metal powder and calcium oxide powder, The average particle size of the active metal powder is 0.5-10 ⁇ m.
  • the mass ratio of the balls in the ball milling process is (7-20):1 and/or at least two grinding balls with different diameters are used in the ball milling.
  • the present invention also provides a fly ash immobilization and stabilization method, which includes:
  • the fly ash is derived from the incineration of industrial, medical and/or domestic waste.
  • the present invention can obtain the following technical effects:
  • the reactive curing stabilizer of the present invention has a specific particle size and microstructure, which can improve the anchoring effect of heavy metal elements in fly ash, especially lead elements. At the same time, due to the use of specific active metal substances, it can also be effective Realize the harmless treatment of organic hazards in fly ash that were difficult to handle in the past;
  • the reactive curing stabilizer of the present invention When used for curing and stabilizing fly ash, it has specific high reactivity to halogenated aromatic compounds such as dioxins or their precursors in the fly ash, and the total removal The rate can reach more than 80%;
  • the preparation process of the reactive curing stabilizer of the present invention can avoid the wall hanging problem that is common in the field, thereby improving the microscopic dispersion structure of the curing stabilizer, and can be produced in an efficient and stable manner;
  • Figure 1 The microscopic morphology of the reactive curing and stabilizing agent of Example 1 of the present invention
  • the "substantially”, “substantially” or “substantially” means that the error is less than 5%, or less than 3%, or less than 1% compared to the related perfect standard or theoretical standard.
  • references to “some specific/preferred embodiments”, “other specific/preferred embodiments”, “embodiments”, etc. refer to the specific elements described in relation to the embodiment (for example, Features, structures, properties, and/or characteristics) are included in at least one of the embodiments described herein, and may or may not be present in other embodiments.
  • the described elements may be combined in various embodiments in any suitable manner.
  • a reactive curing and stabilizing composition for fly ash which is characterized in that the composition includes an active metal and calcium oxide.
  • the active metals that can be used in the present invention may be those metals that have catalytic conversion activity for halides, especially aromatic halides. Therefore, in some specific embodiments of the present invention, the active metal is selected from one or more of aluminum, iron and magnesium.
  • the respective pure metals may be used alone, or metallic materials with a purity of 95% or more, preferably 98% or more.
  • the active metal may be metal aluminum or metal iron alone.
  • mixtures or alloys of these metals can also be used.
  • the content of metallic aluminum or metallic element aluminum is preferably 70% or more, preferably 75% or more, more preferably 80% or more, and more preferably 90% or more.
  • the source of the active metal of the present invention is not particularly limited, and it can be various commercially available metal powders.
  • these metal powders have an average particle size of 0.5-10 ⁇ m. From the viewpoints of processability and storage properties, they are preferred In particular, metal powder with an average particle diameter of 1 to 3 ⁇ m can be used.
  • the calcium oxide that can be used in the present invention is not particularly limited, and various commercially available calcium oxide blocks, granules, or powders can be used.
  • calcium oxide powder from the viewpoint of processability, especially from the convenience of dispersing the metal in the composition.
  • a powder in some specific embodiments of the present invention, it may have an average particle size of 1-15 ⁇ m, preferably 2-10 ⁇ m.
  • the purity of calcium oxide suitable for the present invention may be 90% or more, preferably 93% or more, and more preferably 97% or more.
  • Other substances that may be contained in calcium oxide are not particularly limited, and may be one or more of calcium hydroxide, calcium oxyhydroxide, calcium carbonate, and the like.
  • the above-mentioned calcium oxide can be pre-treated before use.
  • a mixed system is formed by mixing components including the above-mentioned active metal and calcium oxide.
  • the content of the active metal is 25-40%, preferably 27-37%; the content of calcium oxide is 60%-75 %, preferably 63 to 73%.
  • the composition is in the form of particles.
  • these particles exist in the form of substantially spherical or ellipsoidal particles, more preferably, These particles are substantially spherical particles.
  • the composition has an average particle size of 100 to 300 nm.
  • the present invention believes that if the average particle size of the particles of the composition is less than 100nm, on the one hand, the reactivity of the particles may be too high, it is difficult to store for a long time, and the utilization rate may decrease due to the agglomeration effect during use.
  • the average particle size of the particles in the composition is higher than 300 nm, there is a concern that the catalytic conversion activity of aromatic halides will be reduced. In some preferred embodiments of the present invention, it is more advantageous to control the average particle size of the composition to 150-250 nm.
  • the present invention is described in the "average particle diameter" in the art may be used a conventional instrument for measuring particle size, D 50, and the count parameter.
  • the average particle size of the above-mentioned composition of the present invention can be obtained by means of ball milling.
  • suitable additives can be added to the mixture system during ball milling.
  • calcium oxide is present as a continuous phase in the final composite granular product. More specifically, it is advantageous for the calcium oxide as the continuous phase to have a layered structure, so that the active metal can be dispersed in the layered structure as the continuous phase.
  • the average particle diameter of the active metal is 10 to 120 nm, preferably 15 to 100 nm, and more preferably 20 to 80 nm.
  • the layer thickness of the layered calcium oxide is 50 to 150 nm, preferably 80 to 120 nm.
  • the longest dimension of the two-dimensional plane of the layered calcium oxide is not particularly limited, but from the viewpoint of ease of processing, it can be controlled to 0.3 to 5 ⁇ m, preferably 0.5 to 1.5 ⁇ m.
  • the second aspect of the present invention there is provided a method for preparing the composition described in the ⁇ first aspect>, more specifically, a method for preparing the above-mentioned granular composition.
  • calcium oxide may preferably be pre-treated before use.
  • the pretreatment means include one or more of heat treatment, sieving and the like.
  • heat treatment is performed to remove excess moisture
  • the temperature of the heat treatment may be between 500 and 900° C.
  • the time of the heat treatment may be between 0.5 and 5 hours to ensure the purity of calcium oxide.
  • drying can be carried out under normal pressure or reduced pressure, and there is no special requirement for the ambient atmosphere. In some specific embodiments, it can be carried out in an atmospheric environment or in the presence of an inert gas.
  • the inert gas is selected from at least one of nitrogen, argon, helium, and the like.
  • the possible agglomeration of the calcium oxide raw material can be crushed or sieved at the same time or after the heat treatment.
  • pre-treatments may also include pre-treatment of the active metal powder, and these pre-treatment means include one or more of drying and demagnetization.
  • the active metal powder and calcium oxide powder are ball milled.
  • the equipment used for the ball mill is not particularly limited, and ordinary commercially available equipment can be used.
  • the ball milling treatment can be carried out in two stages.
  • the active metal powder and calcium oxide powder can be separately ball-milled, and then in the second stage, the two ball-milling components are mixed into the same ball-milling equipment for mixing and ball-milling to obtain the desired microscopic morphology and average. Particle size.
  • metal powder and calcium oxide powder in the ball milling process, can be mixed in advance, and then placed in a ball milling device for ball milling Process to obtain the desired microscopic morphology and average particle size.
  • the ball milling treatment is carried out in the presence of grinding balls, preferably, dry milling in the absence of other solvent media.
  • the ball-to-material ratio (mass ratio) in the ball milling process is (7-20):1, preferably 8-15:1.
  • the ball-to-material ratio is the ratio of the total mass of the grinding balls used in the ball milling process to the mass of the processed raw materials. In some specific embodiments, it may be the ratio of the total mass of the grinding balls used in the ball milling process to the total mass of the following components: calcium oxide, active metals and optional additives.
  • the amount of grinding balls is too high, which may result in the failure to form the desired microscopic dispersion form, and also reduce the processing volume of the composition for each ball milling treatment, thereby reducing the processing efficiency; too low the amount of grinding balls may result in failure to form The desired microscopic dispersion morphology and average particle size.
  • the effective ball milling time in the above two treatment methods, should be no less than 30 minutes and no more than 300 minutes, and more preferably 40-100 minutes.
  • the "effective ball milling time" in the first ball milling method refers to the total time when the grinding ball contacts one of the two components of metal aluminum powder and calcium oxide powder (first stage + second stage)
  • the treatment time is relatively short; in the second ball milling method, it refers to the ball milling time after the two components are mixed.
  • the ball milling speed is 300 rpm to 1000 rpm, preferably 600 rpm to 800 rpm during each ball milling.
  • the positive and negative rotation can be selected alternately, and the continuous operation and pause cooling time can be set to prevent the internal overheating of the ball mill from affecting the dispersion or activity of the active metal.
  • the types of grinding balls that can be used in the present invention are not particularly limited, and may be zirconium oxide, silicon carbide, or silicon nitride, and zirconium oxide is preferred.
  • the specifications of the grinding balls that can be used for the ball milling treatment are not particularly limited.
  • the present invention has also unexpectedly discovered that when two or more grinding balls of different sizes are used for ball milling, it is more conducive to obtain the desired dispersed form of active metal and calcium oxide in the present invention. Although the mechanism is not completely clear, it is speculated that the use of grinding balls of different sizes can facilitate the pulverization and dispersion of raw materials, especially the pulverization and dispersion of active metal powder raw materials.
  • grinding balls of two sizes can be used at the same time.
  • the diameter of the grinding ball with a smaller size may be 1 to 5 mm, and the diameter of the grinding ball with a larger size may be greater than 5 mm and less than 10 mm.
  • the total volume of small-size grinding balls V1: the total volume of large-size grinding balls V2 is in the range of 10:1 to 1:10.
  • additives may also be used in the ball mill.
  • the use of the addition needs to consider two factors, that is, the added additives help the mixing and dispersion of the mixed components.
  • the added additives it should be avoided because these additives themselves may have lubricating properties. It hinders the mixing of the components, especially the active metal powder.
  • the additives that can be used for these are selected from amphiphilic compounds having a hydrophobic organic group part and a hydrophilic group part.
  • the organic group includes a substituted or unsubstituted hydrocarbyl group.
  • the hydrocarbyl group in some specific embodiments of the present invention, it includes a linear or branched aliphatic hydrocarbyl group with 8 to 30 carbon atoms, preferably a linear or branched chain with 10 to 25 carbon atoms.
  • the aliphatic hydrocarbon group may be saturated or unsaturated.
  • one or more of halogens can be selected in some specific embodiments.
  • the hydrophilic group may be a carboxyl group, an amino group, a sulfonic acid group or a salt thereof, preferably a carboxyl group or a sulfonic acid group and a salt thereof.
  • the additives that can be used can be selected from one or more of long-chain fatty acids or their salts, typically, such as stearic acid or their salts.
  • the amount of these additives may be 2% or less of the total mass of the ball-milled composition, preferably 1.8% or less, and 0.1% or more, preferably 0.3% or more.
  • the above additives there is no particular limitation on the way of using the above additives.
  • the first ball milling method of the present invention it can be preliminarily brought into contact with the active metal powder and ball milled, or the ball milled active metal powder can be mixed with calcium oxide powder and then added to the mixing system.
  • the ball milling is carried out in the presence of two different grinding balls and using the above-mentioned additives.
  • it is not only easier to obtain the desired dispersion of active metals and calcium oxide in the present invention.
  • the state and the satisfactory average particle size can also effectively avoid the excessive cold welding and wall hanging phenomenon that often occurred in the ball milling process in the past, thereby improving the stability and reliability of the entire ball milling process.
  • the above-mentioned ball milling process of the present invention is preferably carried out under the protection of inert gas.
  • inert gas is usually introduced It is considered advantageous to provide protection.
  • the presence of inert gas can also avoid the occurrence of explosion.
  • the inert gas is not particularly limited, and at least one of nitrogen, argon, and helium can be selected.
  • the present invention has no special restrictions on the storage conditions of the reactive curing and stabilizing composition particles. , Can be stored under natural conditions. It is speculated that these preferred technical solutions can realize the dispersion of the active metal more efficiently at the microscopic level, so that the contact between the active metal and the oxygen in the atmosphere is properly isolated by the calcium oxide component. This is in industrial production. It is very advantageous and can greatly simplify storage conditions.
  • the reactive curing and stable composition particles can be stored in an air atmosphere, normal temperature, normal pressure, and daily humidity.
  • the reactive curing and stable composition particles are preferably stored after packaging.
  • the present invention has no special restrictions on the packaging, and only a packaging technical solution that is well known to those skilled in the art that can reduce the interference of impurities such as dust in natural conditions is adopted.
  • the third aspect of the present invention relates to the application of the reactive curing and stable composition obtained in the above ⁇ first aspect> or the ⁇ second aspect>.
  • composition of the present invention has a variety of uses, for example, it can also be used in repairing complex contaminated soil or processing wastes containing heavy metals and/or toxic organics.
  • the present invention does not have special limitations on such application methods, and it is sufficient to use a technical solution for remediation of contaminated soil or a technical solution for waste treatment, which is well-known to those skilled in the art.
  • the reactive curing and stabilizing composition provided by the present invention is used to remediate composite contaminated soil, the mass ratio of the nano-dispersed mixture to the composite contaminated soil is preferably 1:(8-10), more preferably 1:9 .
  • the present invention has also unexpectedly discovered that the reactive curing and stable composition particles of the present invention not only exhibit resistance to heavy metal elements including lead (Cu , Zn, Cr, Cd and/or Ni, etc.) have excellent fixability (over 99%, preferably over 99.9%), especially for harmful organic substances in fly ash that were previously difficult to handle, such as dioxins or Aromatic halides such as its precursors also exhibit specific catalytic conversion efficiency.
  • heavy metal elements including lead (Cu , Zn, Cr, Cd and/or Ni, etc.) have excellent fixability (over 99%, preferably over 99.9%), especially for harmful organic substances in fly ash that were previously difficult to handle, such as dioxins or Aromatic halides such as its precursors also exhibit specific catalytic conversion efficiency.
  • aromatic halides include, but are not limited to, one or more of dioxins, chlorobenzenes, and polychlorinated biphenyls.
  • the total removal rate of these harmful organic compounds in the fly ash can reach 80% or more, preferably 82% or more, and more preferably 85% above. This may be because in the reactive curing and stable composition obtained in the present invention, the active metal is better dispersed in the layered calcium oxide, thereby generating more reaction sites, which can efficiently decompose and break the carbon-halogen bond .
  • the method of treating fly ash using the reactive curing and stabilizing composition of the present invention may specifically include the step of contacting the particles of the composition with the fly ash and the step of mixing.
  • the dosage of the reactive curing and stabilizing composition in some specific embodiments of the present invention, it may be 2-20% of the mass of the fly ash to be treated, preferably 5-15%. If the dosage is too high, the treatment efficiency will have a marginal effect, which will damage the economy. If the dosage is too low, there is a concern that the fixing ability of heavy metal elements, especially the catalytic conversion ability of harmful organic compounds will be reduced.
  • an appropriate amount of water may be added to the fly ash to improve the use effect of the reactive curing and stable composition.
  • the way of adding water is not particularly limited, preferably it can be implemented by spraying, and the total amount of water is 0.05ml water/g fly ash or more and 0.5ml water/g fly ash in terms of fly ash mass.
  • the above-mentioned fly ash mixed with the reactive curing and stabilizing composition of the present invention can be added to a mixer for stirring and mixing.
  • water can be added before and/or during the stirring to make the reactive curing and stable composition of the present invention better mix with fly ash.
  • the present invention has also unexpectedly discovered that, in contrast to the conventional reactive components containing active metal components that require inert gas protection during use, the present invention does not require the use of inert gas even when the above-mentioned stirring treatment is carried out in a stirring device. Protect and still get satisfactory results. It is also presumed to be related to the microscopic dispersion morphology of the reactive curing and stabilizing composition of the present invention.
  • fly ash there is no particular limitation on the source of the above-mentioned fly ash in the present invention, and it can be the incineration of municipal solid waste or the incineration of hazardous waste generated in industrial production or medical treatment.
  • the calcium oxide, aluminum powder, and stearic acid used were all purchased from Aladdin;
  • the fly ash used comes from four domestic waste incineration plants in North China and East China;
  • German Flying Spur P7 enhanced planetary high-energy ball mill
  • the heavy metal detection method adopts HJ/T300;
  • the organic matter test method refers to the test method of chlorinated organic matter in soil sediment.
  • the grinding ball adopts two sizes of mixed grinding balls (the diameter of the ball is 3mm and the diameter of the ball is 8mm in a volume ratio of 9:1 Mixed use), the ball-to-material ratio is 10:1, the ball milling speed is 600rpm, the ball milling program is: run for 3 minutes, pause cooling for 2 minutes, rotate forward and backward alternately for 20 cycles, and the effective ball milling time is 60 minutes.
  • the particles obtained by ball milling were analyzed by scanning electron microscope, as shown in Figure 1 and Figure 2.
  • the concentration of Cu in the leaching solution is 0.008mg/L, the concentration of Zn is lower than the detection line, the concentration of Pb is lower than the detection line, the concentration of Cd is lower than the detection line, the concentration of Cr is lower than the detection line, and the concentration of Ni is lower than the detection line.
  • the removal rate of chlorinated organics in fly ash was 82.43%.
  • the grinding balls adopt two sizes of mixed grinding balls, (3mm diameter balls and 10mm diameter balls are mixed in a volume ratio of 10:1 ), the ball-to-material ratio is 20:1, the ball milling speed is 500rpm, the ball milling program is: run for 3min, pause cooling for 2min, alternate forward and reverse rotation for 40 cycles, and the effective ball milling time is 120min.
  • the leaching concentration of heavy metals and the content of chlorinated organics in the solidified and stabilized incineration fly ash were tested.
  • the HJ/T300 test method was used for the leaching of heavy metals. The results are as follows:
  • the concentration of Cu in the leachate is 0.0105mg/L, the concentration of Zn is lower than the detection line, the concentration of Pb is 0.037mg/L, the concentration of Cd is lower than the detection line, the concentration of Cr is lower than the detection line, and the concentration of Ni is lower than the detection line.
  • the removal rate of chlorinated organics in fly ash was 82.14%.
  • the concentration of Cu in the leaching solution is 0.020mg/L, the concentration of Zn is 0.028mg/L, the concentration of Pb is 1.500mg/L, the concentration of Cd is lower than the detection line, the concentration of Cr is lower than the detection line, and the concentration of Ni is lower than Test line.
  • the removal rate of chlorinated organics in fly ash was 78.19%.
  • the calcium oxide reactive curing and stabilizing agent is added to the domestic waste incineration fly ash at an addition ratio of 10%, and water is sprayed in the amount of 0.1ml/g (water/fly ash) for mixing and curing for 24 hours to complete the curing and stabilization process.
  • the HJ/T300 test method is used for the leaching of heavy metals.
  • the concentration of Cu in the leaching solution is 0.069mg/L, the concentration of Zn is 0.362mg/L, the concentration of Pb is 9.752mg/L, the concentration of Cd is lower than the detection line, the concentration of Cr is 0.287mg/L, and the concentration of Ni is 0.003mg/L.
  • the reactive curing stabilizer composition of the present invention can be produced industrially and used for the immobilization treatment of materials such as fly ash.

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Abstract

一种反应型固化稳定组合物及其制备方法和应用，所述组合物包括活性金属以及氧化钙，所述活性金属选自铝、铁和镁中的一种或多种，所述组合物具有100～300nm的平均粒径，所述活性金属分散于作为连续相的层状氧化钙中，并且所述活性金属的平均粒径为10～120nm，所述层状氧化钙的层厚为50～150nm。

Description

反应型固化稳定组合物及其制备方法和应用 技术领域
本发明属于环保领域，涉及对废物或污染物处理，更具体而言，本发明属于飞灰固化稳定化污染控制领域，具体涉及一种固化稳定化组分及其制备方法以及固定飞灰中重金属与有害有机化合物同步解毒的方法。
背景技术
生活垃圾焚烧技术从20世纪90年代后期在中国得到运用，自2010年以来发展尤为迅速。随着城镇化进程的不断推进，中国的生活垃圾焚烧处理能力已达到36.5万吨/天(2018)(45.65万吨/天，2019)，目前超过44.6％(50.47％，2019)的城市生活垃圾采用焚烧技术进行处理。
与此同时，经估算生活垃圾焚烧厂烟气净化系统产生的飞灰可达490万吨/年。生活垃圾焚烧飞灰具有颗粒小、孔隙度大、碱性强的特点，含有大量的重金属及持久性有机污染物，包括二恶英类、氯苯类、多氯联苯类等，环境风险高，在我国作为名录危险废物进行管理。
目前常用的飞灰处理方式包括了固化/稳定化处理，其中，水泥是常见的固化处理剂，工程中常用水泥对燃烧飞灰进行固化处理，飞灰被掺入到水泥基质后，在一定条件下，经过一定的物理、化学作用，使得有害物质在水泥基质中的浸出和迁移率减小。
此外，也另外开发了其他的固化剂或稳定剂，例如参考文献1公开了一种垃圾焚烧飞灰固化剂，其每100份由80～95份的黄铁矿和5～20份的碳酸钙粉混合制备而成。利用该固化剂对垃圾焚烧飞灰进行处理，可使垃圾飞灰中的有害物质(包括重金属、砷、氟等)得到有效的固化并且固化龄期短。参考文献2公开了一种飞灰固化重金属螯合剂，其包括由以下重量份的原料制成：聚羧酸铵盐20-40份、二巯基乙胺盐酸盐20-30份、氨基甲烷醋酸盐15-25份、硫代乙酸盐10-20份、水30-50份、表面活性剂5-10份。该螯合剂螯合能力强、 热稳定性好以及制备方便。
同时，在我国，目前生活垃圾焚烧飞灰经固化稳定化后进入生活垃圾填埋场分区填埋为最主要的处理方式，能够有效控制大多数重金属浸出达到生活垃圾焚烧飞灰经豁免进入生活垃圾填埋场的入场标准，但也存在对于铅等有害元素的固定能力尚待进一步改进，有时较难达到入场浸出毒性浓度要求。
此外，采用水泥固化或螯合剂稳定化的处理方式无法降解、去除持久性有机污染物，且由于其脂溶性强，不易被无机矿物结构固定，在填埋场堆放填埋过程中逐步迁移进入大气、地下水及土壤中。
参考文献3公开了一种纳米分散混合体的制备方法与应用，由铝粉与氧化钙制备的纳米分散混合体可应用于重金属与有机物的复合污染土壤中，但其在实际制备中存在冷焊结块的问题，并且尚无针对此类纳米分散混合体应用于飞灰中的研究与尝试。
可见，虽然已经对于飞灰的固化，尤其是对其中的有害物质的固定或稳定化处理进行了研究，但对于重金属物质的锚定尤其是对铅元素的锚定以及同时兼顾有机危害物的无害化处理方面仍然具有进一步提高的空间。
参考文献：
参考文献1：CN110279975A
参考文献2：CN110302491A
参考文献3：CN107254316A
发明内容
发明要解决的问题
针对本领域对于飞灰处理存在的上述状况或问题，本发明所要解决的技术问题首先在于提供一种特别适用于飞灰的反应型固化稳定组合物，所述组合物包括活性金属以及氧化钙，所述组合物具有100～300nm的平均粒径，并且所述活性金属分散于作为连续相的层状氧化钙中，通过特定的粒径和微观结构的形成，能够提高组合物对飞灰中重金属元素尤其是铅元素的锚定作用， 同时，由于采用特定的活性金属物质，能够有效实现对飞灰中以往难以处理的有机危害物，尤其是二恶英类物质或其前体类物质进行无害化处理。
此外，本发明的另外一个目的还在于提供一种稳定、高效的制备上述反应型固化稳定剂的方法。
另外本发明还在于提供一种使用上述反应型固化稳定剂处理飞灰的方法。
用于解决问题的方案
通过本发明发明人的潜心研究，发现通过如下的技术方案能够解决上述技术问题：
[1].本发明首先提供了一种反应型固化稳定组合物，所述组合物包括活性金属以及氧化钙，所述活性金属选自铝、铁和镁中的一种或多种，
所述组合物具有100～300nm的平均粒径，所述活性金属分散于作为连续相的层状氧化钙中，并且
所述活性金属的平均粒径为10～120nm，所述层状氧化钙的层厚为50～150nm。
[2].根据[1]所述的组合物，以所述组合物的总质量记，所述活性金属的含量为25％～40％，所述氧化钙的含量为60％～75％。
[3].根据[1]或[2]所述的组合物，所述活性金属中，以活性金属的总质量计，铝的含量为70％以上。
[4].根据[1]～[3]任一项所述的组合物，所述组合物还包括添加剂，所述添加剂为具有疏水有机基团部分和亲水基团部分的两亲性化合物，所述疏水有机基团包括取代或未取代的烃基基团。
[5].进一步，本发明提供了一种根据[1]～[4]任一项所述的组合物的制备方法，所述方法包括：将活性金属粉末与氧化钙粉末进行球磨的步骤，所述活性金属粉末的平均粒径为0.5～10μm。
[6].根据[5]所述的方法，所述球磨中，球磨过程的球料质量比为(7～20)：1和/或所述球磨中至少使用两种直径不同的研磨球。
[7].根据[5]或[6]所述的方法，所述球磨在添加剂的存在下进行，所述添加剂为具有疏水有机基团部分和亲水基团部分的两亲化合物，所述添加剂的用量为球磨原料总重量的0.1～2％。
[8].根据[5]～[7]任一项所述的方法，所述球磨在惰性气体存在的条件下进行。
[9].此外，本发明还提供了一种飞灰固定稳定化方法，所述方法包括：
将根据[1]～[4]任一项所述的组合物与飞灰接触的步骤。
[10].根据[9]所述的方法，所述飞灰源自于工业、医疗和/或生活垃圾的焚烧。
发明的效果
通过上述技术方案的实施，本发明能够获得如下的技术效果：
(1)本发明的反应型固化稳定剂具有特定的粒径和微观结构，够提高飞灰中重金属元素尤其是针对铅元素的锚定作用，同时，由于采用特定的活性金属物质，也能够有效实现对飞灰中以往难以处理的有机危害物进行无害化处理；
(2)在使用本发明的反应型固化稳定剂对飞灰进行固化稳定处理时，对飞灰中存在的二恶英或其前体等卤代芳烃化合物具有特异性的高反应活性，总去除率可以达到80％以上；
(3)本发明的反应型固化稳定剂制备工艺简单，条件要求不高，同时获得的反应型固化稳定剂颗粒产品甚至无需在惰性气体的保护下进行保存和使用，更加适合工业化生产；
(4)本发明的反应型固化稳定剂制备工艺能够避免本领域常见的挂壁的问题，从而在改善了所述固化稳定剂的微观分散结构的同时，能够以高效、稳定的方式进行生产；
附图说明
图1：本发明实施例1的反应型固化稳定化药剂的微观形貌
图2：本发明实施例1的反应型固化稳定化药剂的元素分布
图3：本发明参考例2的纳米分散混合体的微观形貌
具体实施方式
以下，针对本发明的内容进行详细说明。以下所记载的技术特征的说明基于本发明的代表性的实施方案、具体例子而进行，但本发明不限定于这些实施方案、具体例子。需要说明的是：
本说明书中，使用“数值A～数值B”表示的数值范围是指包含端点数值A、B的范围。
本说明书中，如没有特殊声明，则“多”、“多种”、“多个”等中的“多”表示2或以上的数值。
本说明书中，所述“基本上”、“大体上”或“实质上”表示于相关的完美标准或理论标准相比，误差在5％以下，或3％以下或1％以下。
本说明书中，如没有特别说明，则“％”均表示质量百分含量。
本说明书中，使用“可以”表示的含义包括了进行某种处理以及不进行某种处理两方面的含义。
本说明书中，“任选的”或“任选地”是指接下来描述的事件或情况可发生或可不发生，并且该描述包括该事件发生的情况和该事件不发生的情况。
本说明书中，所提及的“一些具体/优选的实施方案”、“另一些具体/优选的实施方案”、“实施方案”等是指所描述的与该实施方案有关的特定要素(例如，特征、结构、性质和/或特性)包括在此处所述的至少一种实施方案中，并且可存在于其它实施方案中或者可不存在于其它实施方案中。另外，应理解，所述要素可以任何合适的方式组合在各种实施方案中。
<第一方面>
本发明的第一方面中，提供了一种用于飞灰的反应型固化稳定组合物，其特征在于，所述组合物包括活性金属以及氧化钙。
活性金属
对于本发明可以使用的活性金属，可以是那些对卤化物，尤其是对芳香族卤化物具有催化转换活性的金属。因此，在本发明一些具体的实施方案中，所述活性金属选自铝、铁和镁中的一种或多种。
对于金属铝、金属铁或金属镁，可以单独地使用各自的纯金属，或者是纯度在95％以上优选为98％以上的金属材料。优选地，从加工性以及催化活性的角度考虑，所述活性金属可以单独的使用金属铝或金属铁。
在本发明另外的一些实施方案中，也可以使用这些金属的混合物或合金。对于金属混合物或合金，以其总质量计，优选的是金属铝或金属元素铝的含量为70％以上，优选为75％以上，进一步优选为80％以上，更优选为90％以上。
另外，对于本发明的活性金属的来源，没有特别的限制，可以是市售的各种金属粉，通常这些金属粉末具有0.5～10μm的平均粒径，从加工性以及保存性的角度考虑，优选地，可以使用平均粒径在1～3μm的金属粉末。
氧化钙
对于本发明中可以使用的氧化钙，没有特别限定，可以使用市售的各种氧化钙块材、颗粒或粉末。
从加工性，尤其是从组合物中金属分散的便利性考虑，优选使用氧化钙粉末。对于这样的粉末，在本发明一些具体的实施方案中，可以具有1～15μm优选具有2～10μm的平均粒径。
此外，对于氧化钙的纯度，适用于本发明的氧化钙纯度可以为90％以上，优选为93％以上，进一步优选为97％以上。对于氧化钙中可能含有的其他物质没有特别限定，可以为氢氧化钙、羟基氧化钙、碳酸钙等的一种或多种。
另外，在本发明一些具体的实施方案中，可以对上述氧化钙在使用前进行前处理。
组合物
本发明中通过将包括上述活性金属以及氧化钙的组分混合形成混合体系。
在本发明一些具体的实施方案中，以所述组合物的总质量计，所述活性金属的含量为25～40％，优选为27～37％；所述氧化钙的含量为60％～75％，优选为63～73％。
在本发明一些具体的实施方案中，所述组合物以颗粒形式存在。对于颗粒的形态没有特别限定，但从加工性以及终端使用性的角度考虑，在本发明一些优选的实施方案中，这些颗粒以基本上为球形或椭球型的颗粒形式存在，更优选地，这些颗粒为基本上球形的颗粒。
在本发明一些具体的实施方案中，所述组合物具有100～300nm的平均粒径。同时本发明认为，如果所述组合物颗粒的平均粒径低于100nm，一方面有可能导致颗粒的反应活性过高，难以长期保存，也可能在使用中出现因为团聚效应而导致的利用率下降的问题；另一方面，如果所述组合物中颗粒的平均粒径高于300nm，则有降低对芳香族卤化物催化转化活性的担忧。在本发明一些优选的实施方案中，将所述组合物的平均粒径控制为150～250nm是更为有利的。
本发明中所述的“平均粒径”可以使用本领域通常的粒度仪进行测量，并且该参数以D 50计。
对于本发明上述组合物的平均粒径，可以通过球磨加工的方式而得到，优选地，可以在球磨加工中，向混合物体系中添加合适的添加剂。
在本发明另外一些优选的具体的实施方案中，最终得到的组合物颗粒产品中，氧化钙作为连续相而存在。更具体而言，作为连续相的氧化钙具有层状结构是有利的，可以使得所述活性金属分散于作为连续相的层状结构中。并且此时，所述活性金属的平均粒径为10～120nm，优选为15～100nm，进一步优选为20～80nm。所述层状氧化钙的层厚为50～150nm，优选为80～120nm。另外，对于层状氧化钙的二维平面最长尺寸，没有特别限定，但从加工的便利性角度而言，可以控制为0.3～5μm，优选为0.5～1.5μm。
<第二方面>
本发明的第二方面中，提供了一种<第一方面>中所述的组合物的制备方 法，更具体的，为上述颗粒状组合物的制备方法。
从有利地形成本发明上文所述的活性金属与氧化钙的微观分散形貌方面考虑，使用球磨的方法对包括活性金属以及氧化钙的组分进行球磨处理是有利的。
如前所述，在本发明一些具体的实施方案中，氧化钙在使用前优选地，可以进行前处理。在一些具体的实施方案中，所述前处理的手段包括热处理、过筛等中的一种或多种。
其中，进行热处理以除去多余的水分，热处理的温度可以在500～900℃之间进行，热处理的时间可以为0.5～5小时，以保证氧化钙的纯度。另外，干燥可以在常压或减压的条件下进行，并且，对于环境氛围，没有特别要求，在一些具体的实施方案中，可以在大气环境或惰性气体的存在下进行。所述惰性气体选自氮气、氩气、氦气等中的至少一种。
另外，任选地，可以在热处理的同时或之后对氧化钙原料可能的团聚进行粉碎或过筛等处理。
其他任选的前处理也可以包括对活性金属粉的前处理，这些前处理手段包括干燥、消磁等中的一种或多种。
进一步，将活性金属粉末与氧化钙粉末进行球磨。对于球磨所使用的设备没有特别的限定，可以使用通常的市售设备。
在本发明一些具体的实施方案中(本发明中也称为第一种球磨方式)，所述球磨处理中，可分为两阶段来进行。第一阶段可以先对活性金属粉末和氧化钙粉末各自单独进行球磨处理，然后在第二阶段中将两种球磨组分混合到同一台球磨设备中进行混合球磨以得到所需的微观形态和平均粒径。
在本发明另外一些具体的实施方案中(本发明中也称为第二种球磨方式)，所述球磨处理中，可以预先将金属粉末与氧化钙粉末进行混合，然后放置于球磨设备中进行球磨处理以得到所需的微观形态和平均粒径。
所述球磨处理在研磨球的存在下进行，优选地，是在无其他溶剂介质存在下的干磨。
在本发明一些具体的实施方案中，球磨处理过程中的球料比(质量比)为(7～20)：1，优选为8～15：1。所述球料比为球磨过程中使用的研磨球的总质量与被处理的原料的质量之比。在一些具体的实施方案中，可以为球磨过程中使用的研磨球的总质量与如下组分的总质量的比：氧化钙、活性金属以及任选的添加剂。
另外，研磨球的用量过高，可能导致无法形成所期望的微观分散形态，并且也导致每次球磨处理的组合物的加工量减少，从而降低加工效率；研磨球的用量过低可能导致无法形成所期望的微观分散形态和平均粒径。
对于球磨的时间，在上述两种处理方式中，有效球磨时间应当不少于30min，并且不超过300min，进一步优选为40～100min。所述“有效球磨时间”在第一种球磨方式中，指的是研磨球接触金属铝粉末和氧化钙粉末两种组分中的某一种组分时(第一阶段+第二阶段)总的处理时间中相对短的时间；在第二种球磨方式中，指的是两种组分混合后的球磨时间。
在本发明的一些具体实施方案中，每次球磨时，球磨速度为300rpm～1000rpm，优选为600rpm～800rpm。同时，还可根据球磨机工作情况选择正反转交替进行，并设置连续运行与暂停冷却时间，以防止球磨设备内部过热影响活性金属的分散性或活性。
另外，本发明可用的有研磨球的种类，没有特别限定，可以为氧化锆、碳化硅或氮化硅，优选为氧化锆。对于球磨处理可以使用的研磨球的规格，原则上没有特别的限定。但同时，本发明也已经意外的发现当使用两种或多种不同尺寸的研磨球共同进行球磨时，更有利于获得本发明所期望的活性金属与氧化钙的分散形态。虽然机理上并不完全清楚，但推测可能是由于，不同尺寸的研磨球的使用能够有利于对原料的粉碎和分散，尤其是有利于对活性金属粉末原料的粉碎和分散。因此，在本发明一些优选的实施方案中，可以同时使用两种尺寸的研磨球。其中，尺寸较小的研磨球的直径可以为1～5mm，尺寸较大的研磨球的直径可以为大于5mm，且在10mm以下。对于两种研磨球的配合使用比例，进一步优选的是，小尺寸研磨球总体积V1：大尺 寸研磨球总体积V2在10：1～1：10的范围内。
此外，为了进一步有利地获得本发明所期望的分散状态，还可以在球磨中使用添加剂。然而，需要说明的是，所述添加的使用需要考虑两方面的因素，即所加入的添加剂有助于混合组分的混合与分散，另外，也要避免因为这些添加剂自身可能具有润滑性质而导致对混合组分、尤其是对活性金属粉末破碎产生阻碍。
因此，在本发明一些具体的实施方案中，对于这些可以使用的添加剂选自具有疏水有机基团部分和亲水基团部分的两亲化合物。并且所述有机基团包括取代或未取代的烃基基团。对于所述烃基基团，在本发明一些具体的实施方案中，包括碳原子数为8～30的直链或支链的脂肪烃基，优选为碳原子数为10～25的直链或支链的脂肪烃基。另外，对于这些烃基可以是饱和的也可以是不饱和的。对于可以使用的取代基，一些具体的实施方案中可以选自卤素中的一种或多种。对于所述亲水基团，可以为羧基、氨基、磺酸基或它们的盐，优选为羧基或磺酸基以及它们的盐。
在本发明一些优选的实施方案中，对于可以使用的添加剂，可以选自长链脂肪酸或其盐中一种或多种，典型地，例如硬脂酸或其盐。
另外，对于这些添加剂的用量，可以为被球磨的组合物的总质量的2％以下，优选为1.8％以下，并且在0.1％以上，优选为0.3％以上。
对于上述添加剂的使用方式，没有特别限定。例如，在本发明上述第一种球磨方式中，可以预先使其与活性金属粉末接触并进行球磨，或者也可以在将球磨过的活性金属粉末与氧化钙粉末混合后再加入到混合体系中进行球磨；在本发明的第二种球磨方式中，同样可以预先使用添加剂预先与未处理的活性金属粉末混合，然后再与氧化钙一起进行球磨，或者也可以在将活性金属粉末与氧化钙粉末混合后再加入到混合体系中进行球磨。
在本发明一些优选的实施方案中，所述球磨在两种不同研磨球以及使用了上述添加剂的存在下进行，其结果，不仅能够更容易地获得本发明所期望的活性金属与氧化钙的分散状态以及满意的平均粒径，同时也能够有效地避 免球磨过程中以往经常出现的过度冷焊和挂壁现象，进而提高了整个球磨过程的稳定性以及可靠性。
另外，本发明上述的球磨过程，优选的是在惰性气体的保护下进行。考虑到球磨过程随着原料的破碎、混合以及研磨球与组分的摩擦将产生大量的热量，导致其中的活性金属组分有被大气氛围中的氧气氧化的过程，因此通常而言导入惰性气体提供保护是被认为有利的。此外，惰性气体的存在也能够避免燃爆的发生。对于惰性气体，没有特别限制，可以选择氮气、氩气和氦气中的至少一种。
通过上述的球磨处理，在球磨结束并降温后得到本发明的反应型固化稳定组合物颗粒。
相对于以往的一些具有活性金属成分的固化稳定剂需要在惰性气体的保护下进行保存以尽可能地保持金属活性，本发明对于所述反应型固化稳定组合物颗粒的储存条件则没有特殊的限定，在自然条件下储存即可。推测可能是由于这些优选的技术方案中，能够在微观上更高效的实现活性金属的分散，使得活性金属与大气中的氧气的接触被氧化钙组分进行了适当的隔绝，这在工业生产上是非常有利的，可以大大简化保存条件。
进一步，在本发明中，所述反应型固化稳定组合物颗粒可以在空气气氛、常温、常压、日常湿度下进行储存。并且，所述反应型固化稳定组合物颗粒优选经包装后储存。本发明对于所述包装没有特殊的限定，采用本领域技术人员熟知的能够减少自然条件中灰尘等杂质干扰的包装的技术方案即可。本发明优选采用本领域技术人员熟知的密封袋对所述纳米分散混合体进行包装后储存。
<第三方面>
本发明的第三方面中，涉及上述<第一方面>中或者是<第二方面>得到的反应型固化稳定组合物的应用。
本发明的上述组合物具有多种用途，例如，还可以在修复复合污染土壤或处理含有重金属和/或毒性有机物的废物中应用。本发明对于这样的应用方 式没有特殊的限定，采用本领域技术人员熟知的应用修复剂对污染土壤进行修复的技术方案或废物处理的技术方案即可。采用本发明提供的反应型固化稳定组合物对复合污染土壤进行修复时，所述纳米分散混合体与所述复合污染土壤的质量比优选为1：(8～10)，更优选为1：9。
进一步，除了上述应用以外，本发明也已经意外的发现，本发明所述的反应型固化稳定组合物颗粒在对飞灰进行固化处理时，不仅表现出了对其中的包括铅的重金属元素(Cu、Zn、Cr、Cd和/或Ni等)具有优异的固定性以外(在99％以上，优选为99.9％以上)，尤其是对飞灰中以往难处理的有害有机物质，例如二恶英或其前体等芳香族卤化物也展现出了特异的催化转换效率。
对于这些芳香族卤化物包括但不限于二恶英类、氯苯类、多氯联苯类化合物等中的一种或多种。在使用本发明的反应型固化稳定组合物对飞灰进行固化稳定处理时，对飞灰中存在这些有害有机化合物的总去除率可以达到80％以上，优选为82％以上，进一步优选为85％以上。这可能是由于在本发明得到的反应型固化稳定组合物中，活性金属更好地分散于层状氧化钙中，进而产生了更多的反应位点，可以高效率地分解、断裂碳卤键。
对于使用本发明的反应型固化稳定组合物对飞灰进行处理的方法没有特别的限制，具体可以包括将所述组合物颗粒与飞灰接触的步骤以及混合的步骤。
对于所述反应型固化稳定组合物的用量，在本发明一些具体的实施方案中，可以为待处理的飞灰质量的2～20％，优选为5～15％。用量过高，处理效率出现边际效应，损害了经济性，用量过低，对于重金属元素的固定能力、尤其是对有害有机化合物的催化转化能力有降低的担忧。
此外，在本发明其他一些具体的实施方案中，可以在将所述组合物颗粒与飞灰接触之前或之后，向飞灰中添加适量的水分以提高反应型固化稳定组合物的使用效果。对于水分的添加方式没有特别限定，优选地可以通过喷洒方式来实施，并且总的水分的用量以飞灰质量计为0.05ml水/g飞灰以上、 0.5ml水/g飞灰以下。
对于上述处理飞灰中可以使用的其他的辅助方法，没有特别限制，例如辅助以适当的搅拌等方法。在本发明一些具体的实施方案中，可以将上述混合了本发明反应型固化稳定组合物飞灰加入到搅拌机中进行搅拌混合。并且，任选地，可以在搅拌前和/或搅拌中加入水以使得本发明的反应型固化稳定组合物更好地与飞灰混合。进一步，本发明也已经意外的发现，相对于以往含有活性金属成分的反应型组分在使用时需要惰性气体保护的情况不同，本发明即使在搅拌设备中进行上述搅拌处理时也无需使用惰性气体保护，并仍然能够获得满意的结果。同样推测是与本发明反应型固化稳定组合物的微观分散形态相关。
此外，对于本发明上述的飞灰的来源，没有特别限制，可以是城市中生活垃圾的焚烧物也可以是工业生产中或医疗产生的有害废物的燃烧物。
实施例
下面结合附图和具体实施例进一步对本发明进行描述。
<原料>：
所采用的氧化钙、铝粉、硬脂酸均为购自阿拉丁；
所采用的飞灰来自华北、华东四个生活垃圾焚烧厂；
<球磨设备>：
德国飞驰P7增强型行星式高能球磨机；
研磨球：氧化锆；
<检测方法>：
重金属检测方法采用HJ/T300；
有机物测试方法参考土壤沉积物中氯代有机物测试方法。
实施例1
30％的铝粉与70％的氧化钙，添加2％的硬脂酸作为球磨过程控制剂，研磨球采用两种尺寸的混合研磨球(直径3mm球与直径8mm球以9：1的体积比混用)，球料比为10：1，球磨转速为600rpm，球磨程序为：运行3min，暂停冷却2min，正反旋转交替进行20个循环周期，有效球磨时间为60min。对球磨得到的颗粒进行扫描电镜分析，如图1和图2。
以上述方式制备反应型固化稳定化药剂，以10％的添加比例加入生活垃圾焚烧飞灰中，以0.1ml/g(水/飞灰)的量喷入水进行混合固化24h，完成固化稳定化过程。
对固化稳定化后的焚烧飞灰重金属浸出浓度和氯代有机物含量进行测试，重金属浸出采用HJ/T300测试方法，氯代有机物经索氏提取后净化浓缩，使用气相色谱质谱联用进行测定。结果如下：
浸出液中Cu的浓度为0.008mg/L，Zn的浓度低于检测线，Pb的浓度低于检测线，Cd的浓度低于检测线，Cr的浓度低于检测线，Ni的浓度低于检测线，均满足生活垃圾焚烧飞灰进入生活垃圾填埋场的入场要求。飞灰中的氯代有机物去除率为82.43％。
实施例2
25％的铝粉与75％的氧化钙，不添加硬脂酸作为球磨过程控制剂，研磨球采用两种尺寸的混合研磨球，(直径3mm球与直径10mm球以10：1的体积比混用)，球料比20：1，球磨转速为500rpm，球磨程序为：运行3min，暂停冷却2min，正反旋转交替进行40个循环周期，有效球磨时间为120min。
以上述方式制备反应型固化稳定化药剂，以5％的添加比例加入生活垃圾焚烧飞灰中，以0.1ml/g(水/飞灰)的量喷入水进行混合固化12h，完成固化稳定化过程。
对固化稳定化后的焚烧飞灰重金属浸出浓度和氯代有机物含量进行测试，重金属浸出采用HJ/T300测试方法，氯代有机物经索氏提取后净化浓缩， 使用气相色谱质谱联用进行测定。结果如下：
浸出液中Cu的浓度为0.0105mg/L，Zn的浓度低于检测线，Pb的浓度为0.037mg/L，Cd的浓度低于检测线，Cr的浓度低于检测线，Ni的浓度低于检测线。飞灰中的氯代有机物去除率为82.14％。
实施例3
40％的铝粉与60％的氧化钙，不添加硬脂酸作为球磨过程控制剂，单一尺寸研磨球(直径5mm)，球料比为7：1，球磨转速为300rpm，球磨程序为：运行3min，暂停冷却2min，正反旋转交替进行10个循环周期，有效球磨时间为30min。
以上述方式制备反应型固化稳定化药剂，以15％的添加比例加入生活垃圾焚烧飞灰中，以0.1ml/g(水/飞灰)的量喷入水进行混合固化48h，完成固化稳定化过程。
浸出液中Cu的浓度为0.020mg/L，Zn的浓度为0.028mg/L，Pb的浓度为1.500mg/L，Cd的浓度低于检测线，Cr的浓度低于检测线，Ni的浓度低于检测线。飞灰中的氯代有机物去除率为78.19％。
参考例1：
以氧化钙反应型固化稳定化药剂，以10％的添加比例加入生活垃圾焚烧飞灰中，以0.1ml/g(水/飞灰)的量喷入水进行混合固化24h，完成固化稳定化过程。
对固化稳定化后的焚烧飞灰重金属Pb浸出浓度，重金属浸出采用HJ/T300测试方法，
浸出液中Cu的浓度为0.069mg/L，Zn的浓度为0.362mg/L，Pb的浓度为9.752mg/L，Cd的浓度低于检测线，Cr的浓度为0.287mg/L，Ni的浓度为0.003mg/L。在对有害有机物的检测中，发现对飞灰中氯代有机物没有去除效果。
参考例2：
重复参考文献3(CN107254316A)中实施例1的制备方法以得到一种纳米分散混合体：
将粒度为1μm的氧化钙粉末在825℃下热处理120min，按质量比Al：CaO＝4：10，将热处理后的氧化钙粉末与粒度为3μm的铝粉混合，在氩气保护下，按球料比20：1，对得到的混合物于500rpm进行240min球磨，得到纳米分散混合体。
对该混合体颗粒进行扫描电镜分析，如图3。
从电镜分析可以看出，本发明的活性金属的分散程度显然优于参考例。
需要说明的是，尽管以具体实例介绍了本发明的技术方案，但本领域技术人员能够理解，本发明应不限于此。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。本文中所用术语的选择，旨在最好地解释各实施例的原理、实际应用或对市场中的技术改进，或者使本技术领域的其它普通技术人员能理解本文披露的各实施例。
产业上的可利用性
本发明的反应型固化稳定剂组合物可以在工业上被生产，并用于飞灰等物质的固定化处理。

Claims (10)

  1. 一种反应型固化稳定组合物，其特征在于，所述组合物包括活性金属以及氧化钙，所述活性金属选自铝、铁和镁中的一种或多种，
    所述组合物具有100～300nm的平均粒径，所述活性金属分散于作为连续相的层状氧化钙中，并且
    所述活性金属的平均粒径为10～120nm，所述层状氧化钙的层厚为50～150nm。
  2. 根据权利要求1所述的组合物，其特征在于，以所述组合物的总质量计，所述活性金属的含量为25％～40％，所述氧化钙的含量为60％～75％。
  3. 根据权利要求1或2所述的组合物，其特征在于，所述活性金属中，以活性金属的总质量计，铝的含量为70％以上。
  4. 根据权利要求1～3任一项所述的组合物，其特征在于，所述组合物还包括添加剂，所述添加剂为具有疏水有机基团部分和亲水基团部分的两亲性化合物，所述疏水有机基团包括取代或未取代的烃基基团。
  5. 根据权利要求1～4任一项所述的组合物的制备方法，其特征在于，所述方法包括：将活性金属粉末与氧化钙粉末进行球磨的步骤，所述活性金属粉末的平均粒径为0.5～10μm。
  6. 根据权利要求5所述的方法，其特征在于，所述球磨中，球磨过程的球料质量比为(7～20)：1和/或在所述球磨中至少使用两种直径不同的研磨球。
  7. 根据权利要求5或6所述的方法，其特征在于，所述球磨在添加剂的存在下进行，所述添加剂为具有疏水有机基团部分和亲水基团部分的两亲性化合物，所述添加剂的用量为被球磨的原料总质量的0.1～2％。
  8. 根据权利要求5～7任一项所述的方法，其特征在于，所述球磨在惰性气体的存在条件下进行。
  9. 一种飞灰固定稳定化方法，其特征在于，所述方法包括：
    将根据权利要求1～4任一项所述的组合物与飞灰接触的步骤。
  10. 根据权利要求9所述的方法，其特征在于，所述飞灰源自于工业、医疗和/或生活垃圾的焚烧。
PCT/CN2021/078042 2020-03-02 2021-02-26 反应型固化稳定组合物及其制备方法和应用 WO2021175156A1 (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114028758A (zh) * 2021-11-19 2022-02-11 中南大学 一种铝灰渣固化稳定化药剂

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111249663B (zh) * 2020-03-02 2021-01-12 清华大学 反应型固化稳定组合物及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060177659A1 (en) * 2005-02-09 2006-08-10 National Pingtung University Of Science & Technology Powder containing carbon nanotube or carbon nanofiber and process for preparing the same
CN104098237A (zh) * 2013-04-10 2014-10-15 阿酷尔商贸（上海）有限公司 污泥或土壤处理方法以及重金属成分稳定化药剂
CN106010544A (zh) * 2016-06-06 2016-10-12 福建省农业科学院土壤肥料研究所 一种含还原铝的复合重金属钝化剂及其使用方法
CN107254316A (zh) * 2017-06-12 2017-10-17 清华大学 一种纳米分散混合体及其制备方法和应用
CN109133290A (zh) * 2018-09-24 2019-01-04 德清县新市乐安污水处理厂 高效处理化工污水的沉淀剂及其制备方法
CN111249663A (zh) * 2020-03-02 2020-06-09 清华大学 反应型固化稳定组合物及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3683025B2 (ja) * 1996-03-14 2005-08-17 奥多摩工業株式会社 廃棄物処理方法
JP2006027944A (ja) * 2004-07-15 2006-02-02 Eco Project:Kk 球状固化物及びその製造方法
CN106377867A (zh) * 2016-08-22 2017-02-08 武汉都市环保工程技术股份有限公司 一种垃圾焚烧飞灰重金属固化剂及其固化方法
CN107057705B (zh) * 2017-05-27 2020-09-22 南京大学（苏州）高新技术研究院 一种重金属污染土壤修复材料、制备方法和用途
CN107876557A (zh) * 2017-06-27 2018-04-06 湖北农谷畅响土壤修复科技股份有限公司 一种用于原位修复砷污染农田土壤的钝化剂及加工方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060177659A1 (en) * 2005-02-09 2006-08-10 National Pingtung University Of Science & Technology Powder containing carbon nanotube or carbon nanofiber and process for preparing the same
CN104098237A (zh) * 2013-04-10 2014-10-15 阿酷尔商贸（上海）有限公司 污泥或土壤处理方法以及重金属成分稳定化药剂
CN106010544A (zh) * 2016-06-06 2016-10-12 福建省农业科学院土壤肥料研究所 一种含还原铝的复合重金属钝化剂及其使用方法
CN107254316A (zh) * 2017-06-12 2017-10-17 清华大学 一种纳米分散混合体及其制备方法和应用
CN109133290A (zh) * 2018-09-24 2019-01-04 德清县新市乐安污水处理厂 高效处理化工污水的沉淀剂及其制备方法
CN111249663A (zh) * 2020-03-02 2020-06-09 清华大学 反应型固化稳定组合物及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANG YUHUI, SHANG YIXUAN, YU SHUYAO, LIU JIANGUO: "Dechlorination of Hexachlorobenzene in Contaminated Soils Using a Nanometallic Al/CaO Dispersion Mixture: Optimization through Response Surface Methodology", INTERNATIONAL JOURNAL OF ENVIRONMENTAL RESEARCH AND PUBLIC HEALTH, vol. 15, no. 5, 27 April 2018 (2018-04-27), XP055841905, DOI: 10.3390/ijerph15050872 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114028758A (zh) * 2021-11-19 2022-02-11 中南大学 一种铝灰渣固化稳定化药剂
CN114028758B (zh) * 2021-11-19 2022-11-04 中南大学 一种铝灰渣固化稳定化药剂

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