CN115780486A - Pollutant nano-resistance control material and preparation method thereof - Google Patents
Pollutant nano-resistance control material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of waste incineration fly ash treatment and resource utilization, and relates to a pollutant nanometer resistance and control material and a preparation method thereof. The material comprises the following raw material components: waste incineration fly ash, a resistance control agent, a resistance control liquid and a metal-based magnetic nano material; the method comprises the following steps: 1) Mixing the waste incineration fly ash, the resistance control liquid, the resistance control agent and the catalyst, and adding the mixture into a high-pressure kettle to perform hydrothermal reaction; 2) After the hydrothermal reaction is finished, the pressure of the high-pressure kettle is relieved to normal pressure in a step-by-step rapid pressure relief mode, solid-liquid separation is carried out on a reaction product, and the obtained solid-phase substance is the pollutant nanometer resistance control material. The invention adopts metal-based magnetic nano materials: the Pd alloy magnetic nano material is used as a catalyst of hydrothermal reaction, modifies heavy metal ions, enables the heavy metal ions to have an ion exchange effect more easily, enhances the capability of preventing and controlling the migration of heavy metals to the outside, and improves the capability of the synthesized product in preventing and controlling the heavy metals in the waste incineration fly ash on a microscopic nano scale.
Description
Technical Field
The invention belongs to the technical field of waste incineration fly ash treatment and resource utilization, and relates to a pollutant nanometer resistance and control material and a preparation method thereof.
Background
After the domestic garbage is incinerated, garbage incineration fly ash is generated in a flue gas purification system, and is listed as dangerous waste (category HW 18) by the nation due to the enrichment of a large amount of toxic and harmful substances such as heavy metals and the like. At present, the main treatment technologies for the waste incineration fly ash comprise: curing techniques, chemical stabilization techniques, heat treatment techniques, and the like. In the solidification technology, the cement solidification technology is one of the most common fly ash solidification technologies, the treatment cost is low, and the fly ash solidification technology has a good stabilizing effect on heavy metals in the fly ash, but after treatment, the solidification body has a large capacity-increasing ratio, and is easy to be corroded by an acidic medium, so that the heavy metals are leached again; chemical agent stabilization techniques such as chelation treatment techniques have a good heavy metal stabilization effect in a short period, but the prepared cured body has poor long-term durability and high cost; in the heat treatment technology, the hydrothermal method has a short reaction period, high curing efficiency and low cost, and thus has become a hot point of many researches.
At present, the hydrothermal method is increasingly applied to solidification stabilization of fly ash, but most of the hydrothermal method is still improvement of a hydrothermal formula and a preparation process, and technologies for optimizing product performance on a micro-nano scale through the hydrothermal method are not many, and researches on modification of heavy metal ions, adjustment of sizes and microstructures of nano crystal particles and the like are rarely reported.
Disclosure of Invention
The invention aims to provide a pollutant nanometer resistance control material and a preparation method thereof.
In one aspect, the invention provides a pollutant nanometer resistance and control material, which comprises the following raw material components: waste incineration fly ash, a resistance control agent, a resistance control liquid and a metal-based magnetic nano material.
In some embodiments, the material comprises the following raw material components in the following weight ratios: the weight ratio of the waste incineration fly ash, the resistance control agent, the resistance control liquid and the metal-based magnetic nano material is 1-10:1-10:20-150:0.1-2.
In some embodiments, the material comprises the following raw material components in weight ratio: the weight ratio of the waste incineration fly ash, the resistance and control agent, the resistance and control liquid to the metal-based magnetic nano material is 3-6:4-7:50-100:0.15-0.4.
In some embodiments, the material comprises the following raw material components in the following weight ratios: the weight ratio of the waste incineration fly ash, the resistance control agent, the resistance control liquid and the metal-based magnetic nano material is 3-6:4-7:50-100:0.15-0.4; preferably, the material comprises the following raw material components in percentage by weight: the weight ratio of the waste incineration fly ash, the resistance and control agent, the resistance and control liquid and the metal-based magnetic nano material is 3:7:50:0.18 of; preferably, the material comprises the following raw material components in percentage by weight: the weight ratio of the waste incineration fly ash, the resistance and control agent, the resistance and control liquid to the metal-based magnetic nano material is 4:6:75:0.26; preferably, the material comprises the following raw material components in percentage by weight: the weight ratio of the waste incineration fly ash, the resistance control agent, the resistance control liquid and the metal-based magnetic nano material is 6:4:100:0.33.
in some embodiments, the material comprises the following raw material components in parts by weight: 1-10 parts of waste incineration fly ash, 1-10 parts of a resistance and control agent, 20-150 parts of a resistance and control liquid and 0.1-2 parts of a metal-based magnetic nano material.
In some embodiments, the material comprises the following raw material components in parts by weight: 3-6 parts of waste incineration fly ash, 4-7 parts of a resistance and control agent, 50-100 parts of a resistance and control liquid and 0.15-0.4 part of a metal-based magnetic nano material.
In some embodiments, the material comprises the following raw material components in parts by weight: 3 parts of waste incineration fly ash, 7 parts of a resistance control agent, 50 parts of a resistance control liquid and 0.18 part of a metal-based magnetic nano material; preferably, the material comprises the following raw material components in parts by weight: 4 parts of waste incineration fly ash, 6 parts of a resistance control agent, 75 parts of a resistance control liquid and 0.26 part of a metal-based magnetic nano material; preferably, the material comprises the following raw material components in parts by weight: 6 parts of waste incineration fly ash, 4 parts of a resistance control agent, 100 parts of a resistance control liquid and 0.33 part of a metal-based magnetic nano material.
In some embodiments, the waste incineration fly ash comprises: the trapped matters of the flue gas purification system and the bottom ash settled at the bottom of the flue and the chimney in the municipal domestic waste incineration disposal process.
In some embodiments, the waste incineration fly ash is obtained by performing grinding pretreatment on dried waste incineration fly ash, and the fineness of the waste incineration fly ash is 300-400 meshes.
In some embodiments, the fineness of the retarder is 300-400 mesh.
In some embodiments, the barrier agent comprises: one or more of metakaolin, furnace slag, alkali slag, fly ash, red mud, silica fume and coal gangue.
In some embodiments, the inhibition and control liquid is prepared by mixing one or more of sodium hydroxide, potassium hydroxide, water glass, sodium carbonate, sodium sulfate and lime with waste alkali liquid according to a liquid-solid ratio of 1.
In some embodiments, the waste lye is an alkaline liquid produced during chemical production, product processing, material cleaning, and the like.
In some embodiments, the metal-based magnetic nanomaterial comprises: pd alloy magnetic nano material; preferably, the model of the Pd alloy magnetic nano material is ZIF-8.
The pollutant nanometer resistance and control material provided by the invention takes waste incineration fly ash as a raw material component, and takes metal-based magnetic nanometer materials: the Pd alloy nano material is used as a catalyst and is synthesized by hydrothermal reaction. The invention relates to a method for preparing a metal-based magnetic nano material by mixing the following components in parts by weight: the Pd alloy nano material is used as a catalyst in the hydrothermal reaction process of the waste incineration fly ash, and can better limit heavy metal pollutants in the waste incineration fly ash in a synthetic product of the hydrothermal reaction through the catalytic action on heavy metal ions in the waste incineration fly ash, prevent and control the heavy metal from migrating to the outside, and further achieve the efficient treatment of the heavy metal ions in the waste incineration fly ash.
On the other hand, the invention also provides a preparation method of the pollutant nanometer resistance and control material, which comprises the following steps:
1) Mixing the waste incineration fly ash, the resistance control liquid, the resistance control agent and the catalyst, and adding the mixture into a high-pressure kettle for hydrothermal reaction;
2) After the hydrothermal reaction is finished, the pressure of the high-pressure kettle is relieved to normal pressure in a step-by-step rapid pressure relief mode, solid-liquid separation is carried out on a reaction product, and the obtained solid-phase substance is the pollutant nanometer resistance control material.
In some embodiments, the catalyst is a metal-based magnetic nanomaterial; preferably, the metal-based magnetic nanomaterial is: pd alloy magnetic nano material; preferably, the model of the Pd alloy magnetic nano material is ZIF-8.
In some embodiments, the mixing ratio by weight of the waste incineration fly ash, the control liquid, the control agent and the catalyst is: 1-10:1-10:20-150:0.1-2.
In some embodiments, the mixing ratio by weight of the waste incineration fly ash, the control liquid, the control agent and the catalyst is: 3-6:4-7:50-100:0.15-0.4.
In some embodiments, the mixing ratio by weight of the waste incineration fly ash, the control liquid, the control agent and the catalyst is: 3:7:50:0.18 of; preferably, the weight mixing ratio of the waste incineration fly ash, the control liquid, the control agent and the catalyst is as follows: 4:6:75:0.26; preferably, the weight mixing ratio of the waste incineration fly ash, the control liquid, the control agent and the catalyst is as follows: 6:4:100:0.33.
in some embodiments, the hydrothermal reaction is: after stirring and mixing at normal temperature, the autoclave is heated and pressurized, and simultaneously magnetic stirring reaction is carried out, and the heating and pressurization are stopped after the reaction is finished, and the reaction is ended.
In some embodiments, the mixing time with stirring at room temperature is: 1-4h.
In some embodiments, the conditions of heating and pressurizing are: 100-350 ℃ and 1-5MPa.
In some embodiments, the magnetic stirring reaction is for a time period of: 24-48h; the rotation number of the magnetic stirring is 40-100r/min.
In some embodiments, the step rapid depressurization is by: and carrying out pressure relief once every 0.1-1.5h, wherein the pressure relief gradient is 10-90% of the current pressure each time until the pressure is reduced to normal pressure.
In some embodiments, the step rapid depressurization is performed by: and carrying out pressure relief once every 0.2-1h, wherein the pressure relief gradient is 25-70% of the current pressure each time until the pressure is reduced to normal pressure.
In some embodiments, the step rapid depressurization is by: carrying out pressure relief once every 0.4-0.6h, wherein the pressure relief gradient is 45% -55% of the current pressure each time until the pressure is reduced to normal pressure; preferably, the step-by-step rapid pressure relief mode is as follows: the pressure relief is carried out every 0.5h, and the pressure relief gradient is 50 percent of the current pressure.
In the method, the metal-based magnetic nano material: after the hydrothermal reaction of the waste incineration fly ash by using the Pd alloy magnetic nano material as the catalyst is finished, the high-pressure kettle is decompressed by adopting the step-by-step rapid decompression mode of the invention, so that the adsorption and fixation capacity of heavy metals in the waste incineration fly ash is further enhanced.
In some embodiments, the solid phase contains more than 90% of crystals having a particle size of 5 to 20 nm.
In the technical scheme disclosed in the prior art, most of metal-based magnetic nano materials are used as an adsorbent, and pollutants such as heavy metals and the like are removed in an adsorption mode, but the metal-based magnetic nano material is prepared by the following steps: on one hand, the Pd alloy magnetic nano material is used as a catalyst in the hydrothermal reaction process of the waste incineration fly ash, so that heavy metal is better limited in a synthetic product of the hydrothermal reaction through the catalytic action of heavy metal ions, and the resistance and control capability of preventing the heavy metal from migrating to the outside is improved; on the other hand, the invention combines a step-by-step rapid pressure relief mode to carry out pressure relief on the high-pressure kettle, so that a synthetic product (nanocrystal) generated by hydrothermal reaction obtains smaller particle size, the nanocrystal with smaller particle size has larger specific surface area, the adsorption effect on pollutants such as heavy metals can be further enhanced, and the treatment efficiency of pollutants such as heavy metals in the waste incineration fly ash can be further improved.
In another aspect, the invention provides the use of said material in a landfill site.
In some embodiments, the landfill comprises: the air exhaust layer and/or the drainage layer and/or the anti-seepage layer and/or the sealing material of the refuse landfill.
The invention also provides application of the method in the aspect of pollutant resource utilization.
In some embodiments, the pollutant comprises waste incineration fly ash.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the resistance and control capacity of the synthesized product to heavy metals in the waste incineration fly ash is optimized and improved on a microscopic nano scale by preparing the heavy metal nano resistance and control material, and the metal-based magnetic nano material is adopted: the Pd alloy magnetic nano material is used as a catalyst of hydrothermal reaction, and heavy metal ions are modified to be easier to generate ion exchange effect, so that the Pd alloy magnetic nano material is limited in nano crystal lattices of synthetic products, and the heavy metal is prevented and controlled from migrating to the outside.
(2) The invention utilizes the mode of high-pressure kettle step-by-step rapid pressure relief to generate more and more tiny nano crystal grains (most of which can reach 5-20 nm), and the nano crystal grains are loosely gathered, thereby greatly increasing the specific surface area of the synthesized product, increasing the nano micropores and further enhancing the adsorption and fixation capacity to the heavy metals in the waste incineration fly ash on the basis of forming a molecular sieve-like structure.
(3) The invention adopts a Pd alloy nano catalyst and a high-pressure kettle step-by-step rapid pressure relief method, and by limiting heavy metal ions in the nano crystal and generating a large amount of nano microcrystals and micropores, the heavy metal in the fly ash is firmly controlled in the nano crystal lattice and the nano micropores. And the formed hydrothermal product can be mixed with materials such as bentonite, landfill leachate and the like for further treatment and then is subjected to resource utilization in a landfill.
Drawings
FIG. 1 shows the pollutant nanometer control material prepared in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention are further illustrated by the following specific examples, which do not represent limitations to the scope of the present invention. Insubstantial modifications and adaptations of the present invention by others of the concepts fall within the scope of the invention.
The source of the waste incineration fly ash as the target treatment substance in the embodiment of the invention comprises: the trapped matters of the flue gas purification system and the bottom ash settled at the bottom of the flue and the chimney in the municipal domestic waste incineration disposal process.
The autoclave used in the examples of the present invention was: the miniature magnetic reaction kettle is KH-50 in model.
The nano resistance control material in the embodiment of the invention refers to: mixing the waste incineration fly ash, the resistance control liquid, the resistance control agent and the catalyst, and adding the mixture into a high-pressure kettle for hydrothermal reaction; after the hydrothermal reaction is finished, the pressure of the high-pressure kettle is relieved to normal pressure in a step-by-step rapid pressure relief mode, solid-liquid separation is carried out on a reaction product, and the obtained solid-phase substance is the nano resistance control material.
The resistance control liquid is: preparing one or more of sodium hydroxide, potassium hydroxide, water glass, sodium carbonate, sodium sulfate and lime with waste alkali liquor according to a liquid-solid ratio of 1.
The Pd alloy magnetic nano material used in the embodiment of the invention is a metal catalyst material, and the model is ZIF-8.
Example 1 preparation method of pollutant nano-resistance control material
(1) Carrying out grinding pretreatment on the dried waste incineration fly ash, wherein the grinding particle size is 300 meshes;
(2) Adding the waste incineration fly ash and the caustic sludge into an autoclave according to the proportion of 3: 1 (weight ratio of sodium hydroxide solution to waste incineration fly ash and caustic sludge) and a catalyst accounting for 0.3 percent of the total mass of all reactants: adding the Pd alloy magnetic nano material into an autoclave, namely: waste incineration fly ash: alkali residue: sodium hydroxide solution: the weight ratio of the catalyst is 3:7:50:0.18 of; stirring and mixing for 2h at normal temperature, heating and pressurizing (150 ℃,2 MPa), simultaneously carrying out magnetic stirring reaction for 24h, wherein the rotation number of the magnetic stirring is 40r/min, stopping heating and pressurizing after the reaction time is over, and terminating the reaction;
(3) And (2) after the reaction is ended, rapidly decompressing the high-pressure kettle step by step once every 0.5 hour, wherein the decompression gradient is 50% of the current pressure each time until the pressure is reduced to normal pressure, taking out a reaction product, performing suction filtration, performing solid-liquid separation to obtain a solid-phase substance 1 and a liquid-phase substance 1, and separating the obtained solid-phase substance 1 to obtain the nano resistance control material.
The obtained solid phase 1 is mixed with bentonite and landfill leachate to prepare a block with the particle size of 2cm, and the block can be used for an exhaust layer of a landfill.
Example 2 preparation method of pollutant nano-resistance control material
(1) Grinding the dry waste incineration fly ash to be pretreated, wherein the ground particle size is 350 meshes;
(2) Adding the waste incineration fly ash and the caustic sludge into an autoclave according to the proportion of 4:1 (weight ratio of sodium hydroxide solution to waste incineration fly ash and caustic sludge) and a catalyst accounting for 0.3 percent of the total mass of all reactants: adding the Pd alloy magnetic nano material into an autoclave, namely: waste incineration fly ash: alkali residue: sodium hydroxide solution: the weight ratio of the catalyst is 4:6:75:0.255; stirring and mixing for 3h at normal temperature, heating and pressurizing (200 ℃,3 MPa), simultaneously carrying out magnetic stirring reaction for 36h, wherein the rotation number of the magnetic stirring is 70r/min, stopping heating and pressurizing after the reaction time is over, and terminating the reaction;
(3) And (2) after the reaction is ended, rapidly decompressing the high-pressure kettle step by step once every 0.5 hour, wherein the decompression gradient is 50% of the current pressure each time until the pressure is reduced to normal pressure, taking out a reaction product, performing suction filtration, performing solid-liquid separation to obtain a solid-phase substance 2 and a liquid-phase substance 2, and separating to obtain the solid-phase substance 2, namely the nano resistance control material.
The obtained solid phase 2 is mixed with diatomite and landfill leachate to prepare a block with the particle size of 3cm, and the block can be used as a drainage layer of a landfill.
Example 3 preparation method of pollutant nano-resistance control material
(1) Carrying out grinding pretreatment on the dried waste incineration fly ash, wherein the ground particle size is 400 meshes;
(2) Adding the waste incineration fly ash and the caustic sludge into an autoclave according to the proportion of 6: 1 (weight ratio of sodium hydroxide solution to waste incineration fly ash and caustic sludge) and a catalyst accounting for 0.3 percent of the total mass of all reactants: adding the Pd alloy magnetic nano material into an autoclave, namely: waste incineration fly ash: alkali residue: sodium hydroxide solution: the weight ratio of the catalyst is 6:4:100:0.33; stirring and mixing for 4h at normal temperature, heating and pressurizing (300 ℃,5 MPa), simultaneously carrying out magnetic stirring reaction for 48h, wherein the rotation number of the magnetic stirring is 100r/min, stopping heating and pressurizing after the reaction time is over, and terminating the reaction;
(3) And (2) after the reaction is ended, rapidly decompressing the high-pressure kettle step by step, and decompressing once every 0.5 hour, wherein the decompression gradient is 50% of the current pressure each time until the pressure is reduced to normal pressure, taking out a reaction product, performing suction filtration, performing solid-liquid separation to obtain a solid-phase substance 3 and a liquid-phase substance 3, and separating the solid-phase substance 3 to obtain the nano resistance control material.
The solid phase 3 is mixed with activated clay and landfill leachate to prepare powder clay with properties, which can be used as an anti-seepage layer or a sealing material of a landfill.
Effect example 1
The solid-phase substance and the liquid-phase substance obtained in the above examples 1 to 3 were subjected to leaching concentration detection of heavy metals and dioxin, wherein the leaching concentration detection of heavy metals was performed on the obtained solid-phase substance and the heavy metals in the liquid-phase substance by a method specified in "solid waste leaching toxicity leaching method acetic acid buffer solution method" (HJ/T300-2007) for 11 kinds of heavy metals specified in GB16889, the limit standard of heavy metals was defined in "pollution control standard for municipal solid waste landfill" (GB 16889-2008), and the concentration detection of dioxin was performed by a method specified in "measurement of dioxins in solid waste" (HJ 77.3-2008). The results are shown in table 1 below:
table 1 examples 1-3 leaching test values of heavy metals and dioxins from solid and liquid substances
Comparative example 1
This comparative example was carried out on the basis of the process of example 2, and differs from example 2 in that, according to a conventional method (without hydrothermal reaction), the reaction mixture was prepared by using a catalyst: the Pd alloy magnetic nano material is used for directly treating fly ash and comprises the following specific steps:
(1) Carrying out grinding pretreatment on the dried waste incineration fly ash, wherein the grinding particle size is 350 meshes;
(2) According to the liquid-solid ratio of 7.5:1, adding water and waste incineration fly ash into an autoclave, then adding a Pd alloy magnetic nano material accounting for 0.3 percent of the total mass into the autoclave, magnetically stirring and reacting for 36 hours at normal temperature with the revolution of 70r/min, taking out a reaction product, carrying out suction filtration, and carrying out solid-liquid separation to obtain a solid phase substance and a liquid phase substance.
Comparative example 2
This comparative example was carried out on the basis of example 2, which differs from example 2 in that: carrying out hydrothermal treatment on the waste incineration fly ash by adopting a hydrothermal method, and adding no catalyst: the Pd alloy magnetic nano material comprises the following specific components:
(1) Carrying out grinding pretreatment on the dried waste incineration fly ash, wherein the grinding particle size is 350 meshes;
(2) Adding waste incineration fly ash and caustic sludge into an autoclave according to a ratio of 4;
(3) And (2) after the reaction is ended, rapidly decompressing step by step, and performing decompression once every 0.5 hour, wherein the decompression gradient is 50% of the current pressure at each time until the pressure is reduced to normal pressure, taking out a reaction product, performing suction filtration, and performing solid-liquid separation to obtain a solid phase substance and a liquid phase substance.
Comparative example 3
This comparative example was carried out on the basis of example 2 and differs from example 2 in that: the added catalyst is different, and the comparative example adopts Fe which is also metal-based nano material 3 O 4 Magnetic nano-meterThe rice material is used as a catalyst, and specifically comprises the following components:
(1) Carrying out grinding pretreatment on the dried waste incineration fly ash, wherein the grinding particle size is 350 meshes;
(2) Adding the waste incineration fly ash and the caustic sludge into the high-pressure kettle according to the proportion of 4:1 adding sodium hydroxide solution and Fe accounting for 0.3 percent of the total mass ratio 3 O 4 Stirring and mixing the magnetic nano material at normal temperature for 3h, heating and pressurizing (200 ℃,3 MPa), simultaneously carrying out magnetic stirring reaction for 36h, wherein the rotation number of the magnetic stirring is 70r/min, stopping heating and pressurizing after the reaction time is over, and terminating the reaction;
(3) And (2) after the reaction is ended, rapidly decompressing step by step, and performing decompression once every 0.5 hour, wherein the decompression gradient is 50% of the current pressure at each time until the pressure is reduced to normal pressure, taking out a reaction product, performing suction filtration, and performing solid-liquid separation to obtain a solid phase substance and a liquid phase substance.
Effect example 2
The solid-phase substance and the liquid-phase substance obtained in the above example 2 and comparative examples 1 to 3 are subjected to heavy metal leaching concentration detection and dioxin concentration detection, the excessive heavy metals cadmium, lead, mercury and dioxin in the fly ash are selected as pollutant indexes to be subjected to leaching concentration detection of the solid-phase substance and the liquid-phase substance in each group, the leaching concentration of the heavy metals is detected, according to the regulation of GB16889, the heavy metals in the obtained solid-phase substance and liquid-phase substance are subjected to leaching concentration test according to the method specified in the acetic acid buffer solution method for leaching toxicity of solid wastes (HJ/T300-2007), the limit value standard of the heavy metals is specified in the pollution control Standard for landfill sites of domestic wastes (GB 16889-2008), and the concentration detection of the dioxin is performed according to the method specified in the determination of dioxin on solid wastes (HJ 77.3-2008). The results are shown in table 2 below:
table 2 table of leaching detection results of heavy metals and dioxin in solid phase and liquid phase in example 2 and comparative examples 1 to 3
As can be seen from the above Table 2, the heavy metal can be well solidified and treated in the example 2, and the leaching concentrations of the solid phase substance and the liquid phase substance both reach the standard limit requirement and are far lower than the standard limit; comparative example 1 has poor adsorption and solidification capacity on heavy metals, and the leaching concentration of the heavy metals is close to that of the original ash; in comparative examples 2 and 3, although the curing capability of part of heavy metals is slightly better, the leaching concentration of cadmium still exceeds the standard.
Comparative example 4
This comparative example was carried out on the basis of example 2, which differs from example 2 in that: the pressure relief modes after the reaction is ended are different, the comparative example adopts step-by-step rapid pressure relief, the pressure relief is carried out once every 0.2 hour, and the pressure relief gradient is 25 percent of the current pressure each time, and the specific steps are as follows:
(1) Carrying out grinding pretreatment on the dried waste incineration fly ash, wherein the grinding particle size is 350 meshes;
(2) Adding the waste incineration fly ash and the resistance control agent into an autoclave according to the proportion of 4: pd alloy magnetic nano material, according to the liquid-solid ratio of 7.5:1, adding the mixture into an autoclave, stirring and mixing the mixture for 3 hours at normal temperature, heating and pressurizing the mixture (200 ℃,3 MPa), simultaneously carrying out magnetic stirring reaction for 36 hours, wherein the rotation number of the magnetic stirring is 70r/min, stopping heating and pressurizing after the reaction time is over, and terminating the reaction;
(3) And (2) after the reaction is ended, rapidly decompressing the high-pressure kettle step by step once every 0.2 hour, wherein the decompression gradient is 25% of the current pressure each time until the pressure is reduced to normal pressure, taking out a reaction product, performing suction filtration, and performing solid-liquid separation to obtain a solid phase substance and a liquid phase substance.
Comparative example 5
This comparative example was carried out on the basis of example 2, which differs from example 2 in that: the pressure relief modes after the reaction is ended are different, the comparative example adopts step-by-step rapid pressure relief, the pressure relief is carried out once every 1 hour, and the pressure relief gradient is 70 percent of the current pressure each time, and the specific steps are as follows:
(1) Grinding the dry waste incineration fly ash to be pretreated, wherein the ground particle size is 350 meshes;
(2) Adding the waste incineration fly ash and the resistance control agent into an autoclave according to the proportion of 4: pd alloy magnetic nano material, according to the liquid-solid ratio of 7.5:1, adding the mixture into an autoclave, stirring and mixing the mixture for 3 hours at normal temperature, heating and pressurizing the mixture (200 ℃,3 MPa), simultaneously carrying out magnetic stirring reaction for 36 hours, wherein the rotation number of the magnetic stirring is 70r/min, stopping heating and pressurizing after the reaction time is over, and terminating the reaction;
(3) And (2) after the reaction is ended, rapidly decompressing the high-pressure kettle step by step once every 1 hour, wherein the decompression gradient is 70% of the current pressure at each time until the pressure is reduced to normal pressure, taking out a reaction product, performing suction filtration, and performing solid-liquid separation to obtain a solid-phase substance and a liquid-phase substance.
Comparative example 6
This comparative example was carried out on the basis of example 2 and differs from example 2 in that: the pressure relief modes after the reaction is ended are different, and the pressure relief of the high-pressure kettle is carried out in a natural cooling mode in the comparative example, which is as follows:
(1) Grinding the dry waste incineration fly ash to be pretreated, wherein the ground particle size is 350 meshes;
(2) Adding the waste incineration fly ash and the resistance control agent into an autoclave according to the proportion of 4: pd alloy magnetic nano material, according to the liquid-solid ratio of 7.5:1, adding the mixture into an autoclave, stirring and mixing the mixture for 3 hours at normal temperature, heating and pressurizing the mixture (200 ℃,3 MPa), simultaneously carrying out magnetic stirring reaction for 36 hours, wherein the revolution of the magnetic stirring is 70r/min, stopping heating and pressurizing after the reaction time is over, and terminating the reaction;
(3) And (2) after the reaction is ended, relieving pressure of the high-pressure kettle in a natural cooling mode until the pressure is reduced to normal pressure, taking out a reaction product, carrying out suction filtration, and carrying out solid-liquid separation to obtain a solid-phase substance and a liquid-phase substance.
Comparative example 7
This comparative example was carried out on the basis of example 2, which differs from example 2 in that: the pressure relief modes after the reaction is ended are different, and the comparative example adopts a one-time rapid pressure relief mode to relieve the pressure of the high-pressure kettle, and comprises the following specific steps:
(1) Grinding the dry waste incineration fly ash to be pretreated, wherein the ground particle size is 350 meshes;
(2) Adding the waste incineration fly ash and the resistance control agent into an autoclave according to the proportion of 4: pd alloy magnetic nano material, according to the liquid-solid ratio of 7.5:1, adding the mixture into an autoclave, stirring and mixing the mixture for 3 hours at normal temperature, heating and pressurizing the mixture (200 ℃,3 MPa), simultaneously carrying out magnetic stirring reaction for 36 hours, wherein the revolution of the magnetic stirring is 70r/min, stopping heating and pressurizing after the reaction time is over, and terminating the reaction;
(3) And (2) after the reaction is ended, relieving the pressure of the high-pressure kettle in a one-time rapid pressure relief mode until the pressure is reduced to normal pressure, taking out a reaction product, carrying out suction filtration, and carrying out solid-liquid separation to obtain a solid-phase substance and a liquid-phase substance.
Effect example 3
The grain sizes (grain size and number) of the solid-phase materials prepared by the methods of example 2, comparative example 4 to comparative example 7 were measured and statistically analyzed, and the grain size was measured by observation with a metallographic microscope and by reference to the method specified in "method for measuring average grain size of metals" (GB/T6394-2002), and the results are shown in table 3:
TABLE 3 grain size and number results of solid phase obtained in example 2 and comparative examples 4 to 7
As can be seen from the above Table 3, the crystal grains with the grain size of 5-20nm formed in the step pressure relief manner in the example 2, the comparative example 4 and the comparative example 5 exceed 75%, wherein the crystal grains with the grain size of 5-20nm in the example 2 reach 91%; the grain with relatively larger grain diameter obtained by the comparative examples 6 and 7 has higher content, wherein in the comparative example 7, the grain with the grain diameter of 30-70nm reaches 86%, and the conventional natural cooling mode adopted by the comparative example 6 can cause the nucleated grain not to continue to perform spontaneous nucleation but to continue to grow on the existing crystal nucleus, so that the micro-nano grain is difficult to generate in the invention. The results show that even if the same hydrothermal reaction conditions are adopted to carry out hydrothermal reaction treatment on the waste incineration fly ash, the performance of the final hydrothermal product is greatly influenced by different pressure relief modes and different parameters in the pressure relief process at different stages. The specific surface area of the crystal generated by the hydrothermal reaction is an important influence factor for adsorbing and stabilizing the heavy metal, and the larger the specific surface area is, the stronger the adsorption stabilizing capability of the crystal on the heavy metal in the waste incineration fly ash is.
Effect example 4
And (3) detecting the leaching concentration of heavy metals and the leaching concentration of dioxin in the solid-phase substance and the liquid-phase substance obtained in the above example 2 and the comparative examples 4 to 7, and selecting standard heavy metals cadmium, lead, mercury and dioxin in the fly ash as pollutant indexes to detect the leaching concentration of the solid-phase substance and the liquid-phase substance in each group, wherein the heavy metal leaching detection is to test the leaching concentration of the heavy metals in the obtained solid-phase substance and the liquid-phase substance according to the method specified in the solid waste leaching toxicity leaching method acetic acid buffer solution method (HJ/T300-2007) according to the regulation of GB16889, and the limit standard of the heavy metals is specified in the pollution control standard of a domestic refuse landfill (GB 16889-2008). The concentration of dioxin was measured by a method specified in "determination of dioxins in solid waste" (HJ 77.3-2008). The results are shown in table 4 below:
table 4 table of leaching detection results of indexes of contaminants in solid phase and liquid phase obtained in example 2 and comparative examples 4 to 7
From the results in table 4, it can be seen that the heavy metal solidification effects of examples 2, comparative examples 4 and 5 are good, and the leaching concentrations can reach the standard limit requirements, while the leaching concentrations of heavy metals such as cadmium and lead in the solid phase obtained in comparative example 6 exceed the standard, and the leaching concentration of cadmium in the solid phase obtained in comparative example 7 exceeds the standard.
Therefore, the specific surface area of the crystal generated by the hydrothermal reaction is an important influence factor for adsorbing and stabilizing the heavy metal, and the larger the specific surface area is, the stronger the adsorption stabilizing capability on the heavy metal in the waste incineration fly ash is. Experiments prove that the autoclave is decompressed by adopting the stepwise rapid decompression mode provided by the embodiment of the invention, more and more tiny nano crystal grains can be generated and are loosely gathered, the specific surface area of a synthesized product is greatly increased on the basis of forming a molecular sieve-like structure, nano micropores are increased, the adsorption and fixation capacity of heavy metals in the waste incineration fly ash can be further increased, and the solidification and stabilization effects of the heavy metals are further enhanced.
And the comparison experiment results further show that the different pressure relief modes and the selection of different parameters in the pressure relief process at different stages not only have great influence on the properties such as the particle size of the final hydrothermal product, but also further influence the treatment effect on the heavy metal in the waste incineration fly ash.
It is to be understood that the present invention has been described with reference to certain embodiments and that various changes in form and details may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A pollutant nanometer resistance and control material is characterized by comprising the following raw material components: waste incineration fly ash, a resistance control agent, a resistance control liquid and a metal-based magnetic nano material.
2. The material according to claim 1, wherein the material comprises the following raw material components in parts by weight: the weight ratio of the waste incineration fly ash, the resistance and control agent, the resistance and control liquid and the metal-based magnetic nano material is 1-10:1-10:20-150:0.1 to 2; preferably, the material comprises the following raw material components in percentage by weight: the weight ratio of the waste incineration fly ash, the resistance and control agent, the resistance and control liquid to the metal-based magnetic nano material is 3-6:4-7:50-100:0.15-0.4; preferably, the material comprises the following raw material components in parts by weight: the weight ratio of the waste incineration fly ash, the resistance control agent, the resistance control liquid and the metal-based magnetic nano material is 3-6:4-7:50-100:0.15-0.4.
3. The material of claim 1, wherein the material comprises the following raw material components in parts by weight: 1-10 parts of waste incineration fly ash, 1-10 parts of a resistance and control agent, 20-150 parts of a resistance and control liquid and 0.1-2 parts of a metal-based magnetic nano material;
preferably, the material comprises the following raw material components in parts by weight: 3-6 parts of waste incineration fly ash, 4-7 parts of a resistance control agent, 50-100 parts of a resistance control liquid and 0.15-0.4 part of a metal-based magnetic nano material.
4. A material according to any one of claims 1 to 3, wherein the waste incineration fly ash comprises: the method comprises the following steps of (1) collecting materials of a flue gas purification system and bottom ash settled at the bottoms of a flue and a chimney in the municipal domestic waste incineration disposal process; preferably, the waste incineration fly ash is obtained by grinding and pretreating dried waste incineration fly ash, and the fineness of the waste incineration fly ash is 300-400 meshes.
5. A material as claimed in any one of claims 1 to 3, wherein the barrier control agent has a fineness of 300 to 400 mesh;
preferably, the barrier agent comprises: one or more of metakaolin, furnace slag, alkali slag, fly ash, red mud, silica fume and coal gangue.
6. The material according to any one of claims 1 to 3, wherein the inhibition and control liquid is obtained by mixing one or more of sodium hydroxide, potassium hydroxide, water glass, sodium carbonate, sodium sulfate and lime with waste alkali liquor according to a liquid-solid ratio of 1; preferably, the waste alkali liquor is alkaline liquid generated in the processes of chemical production, product processing, material cleaning and the like.
7. The material of any one of claims 1-3, wherein the metal-based magnetic nanomaterial comprises: pd alloy magnetic nano material; preferably, the model of the Pd alloy magnetic nano material is ZIF-8.
8. A preparation method of a pollutant nanometer resistance and control material is characterized by comprising the following steps:
1) Mixing the waste incineration fly ash, the resistance control liquid, the resistance control agent and the catalyst, and adding the mixture into a high-pressure kettle for hydrothermal reaction;
2) After the hydrothermal reaction is finished, the pressure of the high-pressure kettle is relieved to normal pressure in a step-by-step rapid pressure relief mode, solid-liquid separation is carried out on a reaction product, and the obtained solid phase substance is the pollutant nanometer resistance and control material.
9. The method of claim 8, wherein the catalyst is a metal-based magnetic nanomaterial; preferably, the metal-based magnetic nanomaterial is: pd alloy magnetic nano material; preferably, the model of the Pd alloy magnetic nano material is ZIF-8;
preferably, the weight mixing ratio of the waste incineration fly ash, the control liquid, the control agent and the catalyst is as follows: 1-10:1-10:20-150:0.1 to 2; preferably, the weight mixing ratio of the waste incineration fly ash, the control liquid, the control agent and the catalyst is as follows: 3-6:4-7:50-100:0.15-0.4;
preferably, the hydrothermal reaction is: stirring and mixing at normal temperature, heating and pressurizing the autoclave, simultaneously performing magnetic stirring reaction, stopping heating and pressurizing after the reaction is finished, and stopping the reaction;
preferably, the time for stirring and mixing at normal temperature is as follows: 1-4h;
preferably, the heating and pressurizing conditions are as follows: 100-350 ℃ and 1-5MPa;
preferably, the magnetic stirring reaction time is as follows: 24-48h; the rotation number of the magnetic stirring is 40-100r/min;
preferably, the step-by-step rapid pressure relief mode is as follows: carrying out pressure relief once every 0.1-1.5h, wherein the pressure relief gradient is 10-90% of the current pressure every time until the pressure is reduced to normal pressure;
preferably, the step-by-step rapid pressure relief mode is as follows: carrying out pressure relief once every 0.2-1h, wherein the pressure relief gradient is 25-70% of the current pressure each time until the pressure is reduced to normal pressure;
preferably, the step-by-step rapid pressure relief mode is as follows: carrying out pressure relief once every 0.4-0.6h, wherein the pressure relief gradient is 45% -55% of the current pressure each time until the pressure is reduced to normal pressure;
preferably, the solid phase contains crystals with a particle size of 5-20nm in an amount of 90% or more.
10. Use of a material according to any one of claims 1 to 7 in a landfill or use of a method according to any one of claims 8 to 9 in the resource utilisation of pollutants;
preferably, the landfill comprises: an exhaust layer and/or a drainage layer and/or an impermeable layer and/or a sealing material of the refuse landfill; preferably, the pollutant comprises waste incineration fly ash.
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