CN112108109A - Preparation method of kaolin-based composite heavy metal additive and product thereof - Google Patents
Preparation method of kaolin-based composite heavy metal additive and product thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a kaolin-based composite heavy metal additive, which comprises the following steps: s1: selecting kaolin as a raw material, crushing and grinding the kaolin to prepare kaolin powder, fully immersing the kaolin powder in an alkaline solution, filtering and drying the solution to obtain alkali modified kaolin; the alkaline solution is Ca (OH)2、NaOne or more solutions of OH, KOH, etc.; s2: and mixing Fe and Ca powder with the alkali modified kaolin, uniformly stirring, calcining at high temperature to generate iron oxide and calcium oxide crystals, and cooling to obtain the required additive. The invention also discloses a kaolin-based composite heavy metal additive. The invention selects alkali modified kaolin powder as the main material of the additive, selects iron powder and calcium powder as the auxiliary materials, prepares the required additive through physical blending-high temperature calcination, has simple operation, and integrates various active components into the composite additive, thereby solving the technical problems of low curing efficiency of the curing additive and cooperative curing of various heavy metals.
Description
Technical Field
The invention belongs to the technical field of heavy metal additives in organic solid waste gasification gas, and particularly relates to a preparation method of a kaolin-based composite heavy metal additive and a product thereof.
Background
The pyrolysis and gasification of the organic solid waste are the most effective way for realizing the resource utilization of the organic solid waste, but the components of the organic solid waste are complex, and contain elements with obvious biotoxicity such As As, Pb, Cd, Cr, Hg and the like, so that the application of the technology is limited. The organic hazardous waste contains almost all heavy metals, wherein the Cd content is 160mg/kg, the As content is 89.4-135mg/kg, the Pb content is 43.6-598mg/kg, and the Hg content is 0.75-7.9 mg/kg. According to the volatilization characteristics, Hg belongs to volatile heavy metals, As, Cd and Pb belong to semi-volatile heavy metals, Cr belongs to nonvolatile heavy metals, and the adoption of a heavy metal curing agent is the main mode for controlling the release of heavy metals.
The adoption of the additive to solidify harmful substances in the organic solid waste into the bottom slag is an effective way for realizing clean utilization of the organic solid waste. In the pyrolysis gasification process, 30% of As, 20-30% of Pb, a small amount of Cr and 13-25% of Cd are released into flue gas. The arsenic discharged is mainly As3+And As5+In the form of toxic As3+>As5+Easy to combine with calcium, aluminum and iron compounds; the discharged lead is PbCl2、PbSO4PbO, mainly Pb2+Form(s) ofExist, easily combine with Si-O and Al-O bonds of silicon-aluminum compounds; cd is easily combined with CaO and the like. In addition, HCl and H in the gasification gas2O、SO2And the like have a significant effect on the solidification of heavy metals.
At present, researchers mainly adopt a mode of adding a certain heavy metal additive to solve the problem of heavy metal solidification in organic solid waste pyrolysis gasification, so that various heavy metals cannot be solidified simultaneously, and the pyrolysis gasification of organic solid waste is the main direction of resource utilization of organic solid waste, so that the development of a compound efficient heavy metal solidification additive aiming at the organic solid waste pyrolysis gasification is a practical need. The method is characterized in that a clean, efficient, cheap and environment-friendly additive is searched, and the method is a hot spot for researching heavy metal control in the organic solid waste gasification process at home and abroad at present; the traditional single curing additive has low efficiency of curing heavy metal, high comprehensive cost and difficult recovery, limits the popularization of the technology, and is difficult to cure the organic solid waste under the multi-working-condition pyrolysis gasification heavy metal in a synergic manner.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a preparation method of a kaolin-based composite heavy metal additive and a product thereof.
To achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a kaolin-based complex heavy metal additive, the method comprising the steps of:
s1: selecting kaolin as a raw material, crushing and grinding the kaolin to prepare kaolin powder, fully immersing the kaolin powder in an alkaline solution, filtering and drying the solution to obtain alkali modified kaolin; the alkaline solution is Ca (OH)2One or more solutions of NaOH, KOH, etc.;
s2: and mixing Fe and Ca powder with the alkali modified kaolin, uniformly stirring, calcining at high temperature to generate iron oxide and calcium oxide crystals, and cooling to obtain the required additive.
Further, in the additive, the mass ratio of the elements of iron, calcium, silicon and aluminum is 0.1-0.15: 0.1-0.2: 1: 1.
further, the kaolin powder has a particle size range of less than 0.1 mm.
Further, the pH of the alkaline solution is greater than 10.
Further, the Fe and Ca powder is powder containing Fe and Ca elements, and Fe in the calcination product at 815 DEG C2O3And the analytical purity of CaO exceeds 80%.
Further, in step S2, the Fe and Ca powders are respectively blended in a proportion of 10 to 15% by mass of the alkali-modified kaolin.
Further, the high-temperature calcination is carried out in a constant-temperature tube furnace, the heating temperature is 700-1300 ℃, and the heat preservation time is 15-30 min.
According to another aspect of the invention, the kaolin-based composite heavy metal additive is prepared according to the preparation method of the kaolin-based composite heavy metal additive, the additive is a mixture of kaolin, iron oxide and calcium oxide, the main components are Al, Si, Ca, Fe and O, the kaolin is a main material of the additive, and iron oxide and calcium oxide crystals generated at high temperature are uniformly dispersed in the additive.
Further, in the additive, the mass ratio of the elements of iron, calcium, silicon and aluminum is 0.1-0.15: 0.1-0.2: 1: 1.
in general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the preparation method of the kaolin-based composite heavy metal additive adopts kaolin As a main material, namely As2O3PbO and the like provide solidification reaction sites, and the thermal stability is good, so that the problems of melting and sintering of the traditional additive under the high-temperature gasification condition are solved; screening for Fe2O3And CaO as an additive, dispersing iron and calcium powder into kaolin by a physical blending-high temperature calcination method, and generating Fe from the calcined auxiliary material component2O3And CaO crystals to obtain the composite curing additive, wherein the active components of the composite curing additive are uniformly dispersed, and the curing activity is higher.
(2) The preparation method of the kaolin-based composite heavy metal additive selects kaolin, CaO and Fe2O3As a composite additive component, the composite additive combines the advantages of three single curing additives, provides curing reaction sites for various heavy metals in the gasified gas, and solves the problem of cooperative curing of various heavy metals in the gasified gas.
(3) The preparation method of the kaolin-based composite heavy metal additive of the invention adds CaO As one of the active components, wherein the CaO has strong As2O3The curing capability and curing efficiency of the CdO are high, and the kaolin can inhibit the agglomeration of CaO particles; by addition of Fe2O3As one of the active components, Fe2O3Having a strong As2O3CdO solidification ability, and Fe2O3The influence of acid gas on the adsorption of heavy metals by the additive can be reduced.
(4) The preparation method of the kaolin-based composite heavy metal additive not only meets the preparation requirement of the additive by controlling the calcination temperature at 700-1300 ℃, but also generates Fe from iron powder2O3The calcium powder generates CaO, the sintering of the additive caused by high temperature is avoided, and the calcination is beneficial to the dispersion and activation of the additive.
(5) According to the preparation method of the kaolin-based composite heavy metal additive, the main material of the additive is alkali modified kaolin powder, the method is simple to operate and easy to control, and the prepared curing additive is high in curing efficiency, wide in application range, low in cost and suitable for industrial popularization.
Drawings
FIG. 1 is a flow chart of a method for preparing a kaolin-based complex heavy metal additive, constructed in accordance with a preferred embodiment of the present invention;
FIG. 2 is a micro-topography of an additive constructed in accordance with a preferred embodiment of the present invention;
FIG. 3 is a graph of the efficiency of the co-solidification of multiple heavy metals in organic solid waste gasification gas constructed in accordance with a preferred embodiment of the present invention.
FIG. 4 is an elemental distribution diagram for the co-solidification of multiple heavy metals in organic solid waste gasification gas constructed in accordance with a preferred embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Fig. 1 is a flow chart illustrating a method for preparing a kaolin-based complex heavy metal additive, constructed according to a preferred embodiment of the present invention, as shown in fig. 1, the method comprising the steps of:
(1) taking kaolin as a raw material, crushing and grinding the kaolin to prepare kaolin powder, fully immersing the kaolin powder in an alkaline solution, filtering and drying to obtain alkali modified kaolin, wherein the particle size range of the kaolin powder is less than 0.1 mm; the alkaline solution is Ca (OH)2NaOH, KOH and the like, and the pH is more than 10;
(2) mixing Fe and Ca powder with alkali modified kaolin, uniformly stirring, calcining at the high temperature of 700-1300 ℃ for 15-30 min in a constant-temperature tubular furnace, generating a large amount of iron oxide and calcium oxide crystals in the composite additive, and cooling to obtain the required additive; fe. And respectively blending the Ca powder according to the proportion of 10-15% of the alkali modified kaolin by mass.
Weighing 40mg of the additive in sequence, putting the additive into a digestion tank, adding 6mL of analytically pure concentrated nitric acid and 2mL of analytically pure hydrofluoric acid, screwing the additive, putting the additive into a microwave digestion furnace, heating the additive at 180 ℃ for 6 hours, naturally cooling the additive, taking the additive out, fixing the volume to 100mL, taking the fixed volume liquid to dilute the fixed volume liquid to an instrument test precision range, performing ICP-OES analysis on the diluted solution, and analyzing to obtain the composite additive with the following elements in mass ratio: 0.1-0.15: 0.1-0.2: 1: 1.
in the step (1), kaolin is used As a main material, and can be As2O3PbO and the like provide solidification reaction sites, have good thermal stability and solve the problems of melting and sintering of the traditional additive under the condition of high-temperature gasification.
In the step (2), CaO is added As one of the active components, and has strong As2O3The curing capability and curing efficiency of the CdO are high, and the kaolin can inhibit the agglomeration of CaO particles; by addition of Fe2O3As one of the active components, Fe2O3Having a strong As2O3CdO solidification ability, and Fe2O3The influence of acid gas on the adsorption of heavy metals by the additive can be reduced.
And by controlling the calcining temperature at 700-1300 ℃, the preparation requirement of the additive is met, and Fe is generated from iron powder2O3The calcium powder generates CaO, the sintering of the additive caused by high temperature is avoided, and the calcination is beneficial to the dispersion and activation of the additive.
The invention discloses a preparation method of a kaolin-based composite heavy metal additive, which adopts kaolin as a main material and screens Fe2O3And CaO as an additive, dispersing iron and calcium powder into kaolin by a physical blending-high temperature calcination method, and generating Fe from the calcined auxiliary material component2O3And CaO crystals to obtain the composite curing additive, wherein the active components of the composite curing additive are uniformly dispersed, and the curing activity is higher. By selecting kaolin, CaO and Fe2O3As a composite additive component, the composite additive combines the advantages of three single curing additives, provides curing reaction sites for various heavy metals in the gasified gas, and solves the problem of cooperative curing of various heavy metals in the gasified gas.
According to the preparation method of the kaolin-based composite heavy metal additive, the main material of the additive is alkali modified kaolin powder, the method is simple to operate and easy to control, and the prepared curing additive is high in curing efficiency, wide in application range, low in cost and suitable for industrial popularization.
According to the preparation method of the kaolin-based composite heavy metal additive, the kaolin component of the curing agent has thermal stability, the alkaline modified kaolin can be well combined with the organic solid waste gasified inorganic mineral bottom slag and can be agglomerated with the bottom slag, the kaolin and the iron oxide and calcium oxide crystals in the additive are not easy to break, the kaolin in the additive and the iron oxide and calcium oxide crystals in the additive are beneficial to directly recycling from the hearth bottom slag, and adsorption sites are provided for curing various heavy metals. The invention solves the problem that various heavy metals are easy to migrate into gasified gas in the gasification process of organic solid waste, provides the additive for efficiently solidifying the heavy metals, can realize the separation of the solidified heavy metals, avoids secondary pollution, has simple operation and easy control, and the prepared curing agent has high solidification efficiency, wide application range, wide sources of 3 raw materials, environmental protection and low price.
The curing properties of the curing agent of the present invention will be better understood with reference to the following specific examples:
example 1
(1) Taking kaolin as a raw material, crushing and grinding the kaolin to prepare kaolin powder, wherein the particle size range of the kaolin powder is less than 0.1mm, and the kaolin powder is fully immersed in Ca (OH) with the pH value of more than 102Filtering and drying the alkaline solution to obtain alkali modified kaolin;
(2) mixing 1g of Fe and 1.2gCa powder with 10g of alkali modified kaolin, uniformly stirring, calcining at 1000 ℃ for 20min in a constant-temperature tubular furnace to generate a large amount of iron oxide and calcium oxide crystals in the composite additive, and cooling to obtain the required additive.
Example 2
(1) Taking kaolin as a raw material, crushing and grinding the kaolin to prepare kaolin powder, fully immersing the kaolin powder in NaOH alkaline solution with the pH value of more than 10, filtering and drying the powder to obtain alkali modified kaolin, wherein the particle size range of the kaolin powder is less than 0.1 mm;
(2) mixing 1.5g of Fe and 1gCa powder with 10g of alkali modified kaolin, uniformly stirring, calcining at the high temperature of 700 ℃ for 30min in a constant-temperature tubular furnace, generating a large amount of iron oxide and calcium oxide crystals in the composite additive, and cooling to obtain the required additive.
Example 3
(1) Taking kaolin as a raw material, crushing and grinding the kaolin to prepare kaolin powder, fully immersing the kaolin powder in KOH alkaline solution with the pH value of more than 10, filtering and drying the powder to obtain alkali modified kaolin, wherein the particle size range of the kaolin powder is less than 0.1 mm;
(2) mixing 1.2g of Fe and 1.5gCa powder with 10g of alkali modified kaolin, stirring uniformly, calcining for 15min at 1300 ℃ in a constant-temperature tubular furnace to generate a large amount of iron oxide and calcium oxide crystals in the composite additive, and cooling to obtain the required additive.
Example 4
(1) Taking kaolin as a raw material, crushing and grinding the kaolin to prepare kaolin powder, fully immersing the kaolin powder in KOH alkaline solution with the pH value of more than 10, filtering and drying the powder to obtain alkali modified kaolin, wherein the particle size range of the kaolin powder is less than 0.1 mm;
(2) mixing 1.3g of Fe and 1.3g of 1.3gCa powder with 10g of alkali modified kaolin, uniformly stirring, calcining at the high temperature of 900 ℃ for 22min in a constant-temperature tubular furnace, generating a large amount of iron oxide and calcium oxide crystals in the composite additive, and cooling to obtain the required additive.
To facilitate a further understanding of the curing properties of the additives of the present invention, the additives of the present invention were subjected to a curing agent microtopography analysis: taking a little of the additive, and analyzing the morphology of the additive particles and the distribution characteristics of the loaded active components by adopting a scanning electron microscope; carrying out a curing agent thermal stability experiment: taking 1g of the curing agent, placing the curing agent in a muffle furnace, keeping the temperature for 1h at the temperature of 800-1300 ℃ at an interval gradient of 100 ℃, taking out a sample, and observing the sintering condition of the sample; carrying out a solidified heavy metal characteristic experiment: taking the additive and organic solid waste raw materials containing known heavy metals according to the weight ratio of 1: 5, uniformly stirring the mixture in a mass ratio, and putting the mixture in a high-temperature gasification reaction furnace to finish CO2Gasifying and testing the curing capability of different heavy metals. Analysis of the distribution characteristics of the solidified heavy metals was also carried out: taking 0.5g of the additive, placing the additive in a heavy metal generating-adsorbing device, taking out the additive to adsorb the heavy metal and performing element distribution analysis.
The method and results are as follows:
FIG. 2 is a micro-topography of an additive constructed in accordance with a preferred embodiment of the present invention, the solidification-additive micro-topography analysis experiment being: a small amount of the additive is taken, the particle morphology and the distribution characteristics of the loaded active components of the additive are analyzed by a scanning electron microscope, and the microscopic morphology is shown in figure 2. As can be seen from the figure, the prepared composite additive has a large number of fine particles on the surface and developed pores.
The experimental result shows that the prepared composite additive has a rough surface, a large number of fine particles and developed pores, and can provide more active sites for gas-phase heavy metal curing.
Further, the additives were subjected to a thermal stability test: 1g of the additive is evenly spread in a crucible in sequence, and then is sent into a high-temperature tube furnace with the temperature of 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃ and 1400 ℃, the temperature is kept for 1h, the crucible is taken out and weighed, and the sintering condition is observed. Results 5 experiments had mass loss percentages as follows: 9.8%, 11.2%, 11.7%, 11.9%, 12.01%, 12.09%, 12.14%, and at 1000-1400 deg.C, considering the high temperature removal of the bound water of kaolin in the additive, and the decomposition of the adsorbed water and carbon dioxide of the additive<The mass loss of 1% results from the mass loss of the additive, the active component, Fe, bound to the additive2O3And CaO in 15%, 20%, whereby the loss of active components can be ignored. The surface of the additive is slightly melted, mainly Fe, through microscopic observation2O3The melting results in agglomeration of the fine particles on the surface of the curing agent.
This experiment demonstrates that the additive of the present invention is stable at high temperature of 1400 deg.C with negligible loss of active ingredient and that the additive is thermally stable.
FIG. 3 is a graph of the efficiency of the co-solidification of multiple heavy metals in organic solid waste gasification gas constructed in accordance with a preferred embodiment of the present invention. The experiment for the characteristic of the additive for curing heavy metal specifically comprises the following steps: taking the additive and organic solid waste raw materials containing known heavy metals according to the weight ratio of 1: 5, uniformly stirring the mixture in a mass ratio, and putting the mixture in a high-temperature gasification reaction furnace to finish CO2Gasifying and testing the curing capability of different heavy metals. The solidification rate of heavy metals in the bottom slag added with the curing agent is shown in figure 3, and the result shows that the heavy metals migrating to the bottom slag in the organic solid waste gasification process under the condition of the additive: pb accounts for 67%84 percent of the additive, 43 percent of As, 83 percent of Cd, 85 percent of Cr and 97 percent of Cd, and the additive has obvious effect of inhibiting the release of heavy metals. The experiment shows that the additive can be used for synergistically solidifying various heavy metals in organic solid waste gasification gas.
FIG. 4 is an elemental distribution diagram for the co-solidification of multiple heavy metals in organic solid waste gasification gas constructed in accordance with a preferred embodiment of the present invention. The experiment of the distribution characteristics of the additive solidified heavy metal specifically comprises the following steps: taking 0.5g of the additive, placing the additive in a heavy metal generating-adsorbing device, simulating the concentration of As in gasified gas to be 100 mu g/g, adsorbing the As at the temperature of 900 ℃, adsorbing for 30min, taking out the additive after adsorbing the As and analyzing the element distribution, wherein the result is shown in figure 4. As can be seen from the figure, As adsorbed by the additive is relatively discrete and uniformly distributed on the surface of the additive. The experiment shows that the additive can uniformly adsorb heavy metal, and the active components of the additive are uniformly distributed.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the kaolin-based composite heavy metal additive is characterized by comprising the following steps:
s1: selecting kaolin as a raw material, crushing and grinding the kaolin to prepare kaolin powder, fully immersing the kaolin powder in an alkaline solution, filtering and drying the solution to obtain alkali modified kaolin; the alkaline solution is Ca (OH)2One or more solutions of NaOH, KOH, etc.;
s2: and mixing Fe and Ca powder with the alkali modified kaolin, uniformly stirring, calcining at high temperature to generate iron oxide and calcium oxide crystals, and cooling to obtain the required additive.
2. The preparation method of the kaolin-based composite heavy metal additive according to claim 1, wherein the mass ratio of the elements of iron, calcium, silicon and aluminum in the additive is 0.1-0.15: 0.1-0.2: 1: 1.
3. the method for preparing the kaolin-based composite heavy metal additive according to claim 1, wherein the kaolin powder has a particle size range of less than 0.1 mm.
4. The method for preparing the kaolin-based complex heavy metal additive according to claim 1, wherein the pH of the alkaline solution is greater than 10.
5. The method for preparing the kaolin-based composite heavy metal additive as claimed in claim 1, wherein the Fe, Ca powder is a powder containing Fe, Ca elements, Fe in the calcined product2O3And the analytical purity of CaO exceeds 80%.
6. The method for preparing the kaolin-based composite heavy metal additive according to claim 1, wherein in step S2, the Fe powder and the Ca powder are respectively blended according to a proportion of 10-15% of the mass of the alkali-modified kaolin.
7. The preparation method of the kaolin-based composite heavy metal additive according to claim 1, wherein the high-temperature calcination is performed in a constant-temperature tubular furnace, the heating temperature is 700-1300 ℃, and the heat preservation time is 15-30 min.
8. The kaolin-based composite heavy metal additive is prepared by the preparation method of the kaolin-based composite heavy metal additive according to any one of claims 1 to 7, and is characterized in that the additive is a mixture of kaolin, iron oxide and calcium oxide, the kaolin is a main material of the additive, and iron oxide and calcium oxide crystals generated at high temperature are uniformly dispersed in the additive.
9. The kaolin-based composite heavy metal additive as claimed in claim 8, wherein the mass ratio of the elements of iron, calcium, silicon and aluminum in the additive is 0.1-0.15: 0.1-0.2: 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011052899.3A CN112108109B (en) | 2020-09-29 | 2020-09-29 | Preparation method of kaolin-based composite heavy metal additive and product thereof |
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