CN111943336A - Method for preparing polysilicate aluminum ferric flocculant, polysilicate aluminum ferric flocculant and application thereof - Google Patents
Method for preparing polysilicate aluminum ferric flocculant, polysilicate aluminum ferric flocculant and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of solid waste resource utilization of a gas flow bed gasification process in the coal chemical industry, in particular to a method for preparing a polysilicate aluminum ferric flocculant, the polysilicate aluminum ferric flocculant and an application thereof, wherein the method comprises the following steps: (1) mixing the gasified residue with an acid solution I, and carrying out a first acid dissolution reaction to obtain an iron-containing filtrate and a filter residue I; (2) mixing the filter residue I with alkaline solids, and roasting and activating to obtain activated slag; (3) mixing the activated slag with an acid solution II, and carrying out a second acid dissolution reaction to obtain a silicon-aluminum-containing filtrate and a filter residue II; (4) and (3) contacting the iron-containing filtrate with the silicon-aluminum-containing filtrate, polymerizing, and then aging to obtain the polysilicate aluminum ferric flocculant. The method realizes the field of using the entrained flow gasification slag to prepare the polyaluminum ferric silicate flocculant, achieves the aim of treating waste by waste, and can be used for treating coal chemical wastewater, mine water or gasified black water.
Description
Technical Field
The invention relates to the technical field of solid waste recycling of a gas flow bed gasification process in the coal chemical industry, in particular to a method for preparing a polysilicate aluminum ferric flocculant, the polysilicate aluminum ferric flocculant and application thereof.
Background
The current resource status of China determines a primary energy consumption structure taking coal as a main body, and the primary energy consumption structure cannot be changed for a long time. With the gradual transition of economic development mode to high-quality development stage in China, the coal clean utilization technology is rapidly developed, and the coal gasification technology is one of the main ways of coal clean utilization.
The entrained flow gasification technology is a process in which coal powder and a gasification medium enter a gasification furnace at the same time and react at a high temperature to generate synthesis gas or coal gas. In the process, the gasified slag is in a molten state under the high-temperature condition, and is discharged out of the gasification furnace after being chilled. The gasification slag mainly contains glassy aluminosilicate, has low chemical activity, and also contains a small amount of unburned carbon. At present, gasification slag is used as common industrial solid waste, and a disposal method of stacking and landfill is mainly adopted, so that a large amount of land resources are occupied, and waste of solid waste resources and environmental pollution are caused.
The polysilicate aluminum ferric flocculant is a novel inorganic polymeric flocculant developed on the basis of aluminum salt, ferric salt and polysilicate flocculant. The polysilicate aluminum ferric flocculant integrates the characteristics of large floc and quick sedimentation of aluminum salt and ferric salt flocculants and the bridging adsorption effect of the polysilicate flocculant, and has the characteristics of stronger stability and excellent coagulation effect. The poly-ferric aluminum silicate flocculant is widely concerned in the research of treating industrial wastewater and mine water.
CN108314071A discloses a method for preparing polyaluminium chloride by using gasification slag, which comprises the following steps: (1) circularly leaching the gasified slag by using hydrochloric acid to obtain aluminum-containing liquid and leached slag; (2) and carrying out post-treatment on the aluminum-containing liquid to obtain the polyaluminum chloride.
However, the utilization amount of the gasified slag generated by the entrained flow bed needs to be further improved, and a utilization channel needs to be developed. In the prior art, no report is found on the technology of applying the entrained flow gasified slag to the preparation of the polysilicate aluminum ferric flocculant.
Disclosure of Invention
The invention aims to overcome the defects of low utilization amount and few application channels of entrained flow bed gasified slag in the prior art, and provides a method for preparing a polysilicate aluminum ferric flocculant, the polysilicate aluminum ferric flocculant and application thereof.
The inventor discovers that after gasification slag is subjected to first acid dissolution reaction, iron-containing filtrate and filter residue I are obtained, the filter residue I is roasted and activated through alkaline solids to obtain activated slag, the activated slag is subjected to second acid dissolution reaction to obtain silicon-aluminum-containing filtrate and filter residue II, the iron-containing filtrate and the silicon-aluminum-containing filtrate are mixed, polymerized and aged, the gasification slag can be used for preparing the polysilicate aluminum ferric flocculant, effective elements in the gasification slag can be maximally utilized through step-by-step extraction, and a silicon source, an aluminum source or an iron source does not need to be additionally added, wherein the alkali solid roasting and activating process can activate aluminosilicate in the gasification slag, and silicon and aluminum elements are more easily dissolved out; the prepared polysilicate aluminum ferric flocculant can be used for primary treatment of coal chemical industry wastewater, mine water or gasified black water.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a polysilicate aluminum ferric flocculant, the method comprising the steps of:
(1) mixing the gasified residue with an acid solution I, and carrying out a first acid dissolution reaction to obtain an iron-containing filtrate and a filter residue I;
(2) mixing the filter residue I with alkaline solids, and roasting and activating to obtain activated slag;
(3) mixing the activated slag with an acid solution II, and carrying out a second acid dissolution reaction to obtain a silicon-aluminum-containing filtrate and a filter residue II;
(4) contacting the iron-containing filtrate with the silicon-aluminum-containing filtrate, polymerizing, and then aging to obtain a polysilicate aluminum ferric flocculant;
optionally, the method further comprises: after the first acid dissolution reaction is carried out, separating the product after the reaction to obtain a first solid product and the iron-containing filtrate, and carrying out first washing on the first solid product to obtain washing liquid I;
optionally, the method further comprises: after the second acid solution reaction is carried out, separating the product after the reaction to obtain a second solid product and the filtrate containing silicon and aluminum, and carrying out second washing on the second solid product to obtain a washing liquid II.
Preferably, the weight ratio of the alkaline solid to the filter residue I in the step (2) is 0.1-0.3.
Preferably, the iron-containing filtrate and the silicon-aluminum-containing filtrate in the step (4) are used in amounts that: the molar ratio of Al/Fe is 0.9-1.1, and the molar ratio of (Al + Fe)/Si is 0.9-1.3.
Preferably, the conditions of the polymerization in step (4) include: the pH value is 3.5-5, the polymerization temperature is 55-80 ℃, and the polymerization time is 1-4 h.
The invention provides a polysilicate aluminum ferric flocculant prepared by the method of the first aspect.
The third aspect of the invention provides an application of the polysilicate aluminum ferric flocculant in the second aspect in treating coal chemical industry wastewater, mine water or gasified black water.
According to the technical scheme, the method can effectively dissolve out iron and silicon-aluminum elements in the gasified slag through step-by-step extraction, is simple in process, mild in condition and high in extraction rate, realizes maximum utilization of the effective elements in the gasified slag, and can prepare the polysilicate aluminum-iron flocculant without additionally adding a silicon source, an aluminum source or an iron source; the prepared polysilicate aluminum ferric flocculant can be used for primary treatment of coal chemical industry wastewater, mine water or gasified black water, has good flocculation effect and stability, and reduces the difficulty of subsequent treatment. The invention achieves the purpose of treating wastes with wastes while improving the high-value and diversified utilization ways of the entrained flow gasification slag.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, the first aspect of the present invention provides a method for preparing a polysilicate aluminum ferric flocculant, the method comprising the steps of:
(1) mixing the gasified residue with an acid solution I, and carrying out a first acid dissolution reaction to obtain an iron-containing filtrate and a filter residue I;
(2) mixing the filter residue I with alkaline solids, and roasting and activating to obtain activated slag;
(3) mixing the activated slag with an acid solution II, and carrying out a second acid dissolution reaction to obtain a silicon-aluminum-containing filtrate and a filter residue II;
(4) contacting the iron-containing filtrate with the silicon-aluminum-containing filtrate, polymerizing, and then aging to obtain a polysilicate aluminum ferric flocculant;
optionally, the method further comprises: after the first acid dissolution reaction is carried out, separating the product after the reaction to obtain a first solid product and the iron-containing filtrate, and carrying out first washing on the first solid product to obtain washing liquid I;
optionally, the method further comprises: after the second acid solution reaction is carried out, separating the product after the reaction to obtain a second solid product and the filtrate containing silicon and aluminum, and carrying out second washing on the second solid product to obtain a washing liquid II.
In the present invention, there is no limitation on the source of the gasified slag, and the gasified slag may be the gasified slag generated after coal is gasified by a gasification apparatus including, but not limited to, an entrained flow bed.
The composition of the gasified slag can be selected in a wide range, and the gasified slag meets the following requirements under the optimal condition: ash component containing SiO2、Al2O3And Fe2O3And SiO2The content is more than or equal to 48 wt%, and Al2O3The content is more than or equal to 18 wt%, Fe2O3The content is more than or equal to 7wt percent, and the carbon residue content of the gasified slag is less than or equal to 3 percent. By adopting the preferred scheme of the invention, the elements of silicon, aluminum and iron in the gasified slag are more favorably and fully utilized.
More preferably, the gasification slag satisfies: ash component containing SiO2、Al2O3And Fe2O3And SiO2The content is more than or equal to 50 wt%, Al2O3The content is more than or equal to 18 wt%, Fe2O3The content is more than or equal to 10wt percent, and the carbon residue content of the gasification slag is less than or equal to 3 percent.
The conditions for the first acid dissolution reaction in the present invention can be selected within a wide range, as long as it is advantageous to dissolve as much iron in the gasified slag as possible. Preferably, the liquid-solid weight ratio of the first acid dissolution reaction in step (1) is 2-6:1, more preferably 2-4: 1.
Preferably, the concentration of the acid solution I in the step (1) is 0.5-1 mol/L.
According to the present invention, preferably, the conditions of the first acid dissolution reaction include: the first reaction time is 60 to 180min, more preferably 60 to 120 min.
In the present invention, the first acid dissolution reaction is preferably performed at room temperature. The specific temperature of the room temperature is not limited in the present invention, and can be freely selected by those skilled in the art according to actual requirements, for example, the room temperature can be (20-40) ° c ± 5 ℃.
Preferably, the first acid dissolution reaction is carried out under stirring at a rate of 20-100rpm, more preferably 20-40 rpm.
In a preferred embodiment of the present invention, the step (1) further comprises: before the mixing, the gasified slag is optionally dried and crushed in sequence, so that the gasified slag can be fully subjected to acid dissolution and alkaline solid roasting activation.
Preferably, the proportion of particles with the particle size less than or equal to 80 meshes in the product obtained after crushing is more than 90 wt%.
In a preferred embodiment of the present invention, the step (1) further comprises: and carrying out first drying on a first solid product obtained after the first washing to obtain the filter residue I.
The conditions of the first drying are not limited in the present invention, and preferably, the first drying is performed so that the moisture content in the residue i is not more than 8 wt%.
Preferably, the detergent used in the first washing is water. In the invention, the water is not limited, and can be unused pure water or production water produced in coal chemical industry production.
In order to fully exert the activation effect of the basic solid roasting on the silicon and aluminum elements in the filter residue I, the weight ratio of the basic solid to the filter residue I in the step (2) is preferably 0.1-0.3.
More preferably, the weight ratio of the alkaline solid to the filter residue I is 0.17-0.3.
The invention has wider selection range of the types of the alkaline solids, and only needs to be beneficial to the activation of silicon and aluminum elements in the filter residue I; preferably, the basic solid is a basic sodium-containing compound and/or a basic potassium-containing compound.
The invention has wider selection range of the alkaline potassium-containing compound, and only needs to be beneficial to improving the flocculation effect; for example, the basic potassium-containing compound may be potassium hydroxide and/or potassium carbonate.
More preferably, the basic solid is a basic sodium-containing compound.
The invention has wider optional range of the alkaline sodium-containing compound, and only needs to be beneficial to improving the flocculation effect; preferably, the basic sodium-containing compound is sodium hydroxide and/or sodium carbonate, more preferably sodium hydroxide.
Preferably, the conditions of the calcination activation include: the roasting temperature is 600-750 ℃, and the roasting time is 60-180min, more preferably 60-120 min.
In order to dissolve silicon and aluminum elements in the activated slag as much as possible, the liquid-solid weight ratio in the second acid solution reaction in the step (3) is 3-8:1, and more preferably 3-6: 1.
Preferably, the concentration of the acid solution II in the step (3) is 0.8-1.3 mol/L.
The invention has wider selection range of the types of the acid solution I and the acid solution II, and only needs to be beneficial to dissolving out silicon, aluminum and iron elements; preferably, the acid solution i and the acid solution ii are each independently selected from a hydrochloric acid solution and/or a sulfuric acid solution.
The sources of the acid solution I and the acid solution II are not limited; preferably, the acid solution I and the acid solution II are respectively and independently selected from at least one of fresh acid, waste acid for production and a solution prepared from acid and a washing liquid, and the washing liquid is the washing liquid I and/or the washing liquid II. More preferably, the acid solution I and the acid solution II are respectively and independently selected from solutions prepared by acid and washing liquid, and the washing liquid is the washing liquid I and/or the washing liquid II so as to prevent wastewater from being discharged.
In the present invention, the fresh acid refers to an unused acid solution, such as an unused hydrochloric acid solution; the production waste acid refers to waste acid generated in industrial production, and preferably waste acid generated in coal chemical production; the solution prepared from the acid and the washing solution refers to a solution prepared from pure acid and the washing solution, for example, a solution prepared from HCl and the washing solution.
The conditions for the second acid dissolution reaction can be selected in a wide range, and only silicon, aluminum and iron elements are favorably dissolved out; preferably, the conditions of the second acid solution reaction in step (3) include: the second reaction time is 60 to 180min, more preferably 60 to 120 min. The second acid solution reaction may be performed at room temperature.
Preferably, the second acid dissolution reaction is carried out with stirring at a rate of 20 to 100rpm, more preferably 20 to 40 rpm.
Preferably, the detergent used in the second washing is water. In the invention, the water is not limited, and can be unused pure water or production water in coal chemical industry production.
In a preferred embodiment of the present invention, the iron-containing filtrate and the silicon-containing aluminum filtrate in step (4) are used in amounts that: the molar ratio of Al/Fe is 0.9-1.1, and the molar ratio of (Al + Fe)/Si is 0.9-1.3. By adopting the preferable technical scheme, the prepared flocculating agent has better coagulation effect.
According to the present invention, it is preferred that no additional aluminum, iron or silicon source is added in step (4).
Preferably, the iron-containing filtrate and the silicon-aluminum-containing filtrate are used in the following amounts: the molar ratio of Al/Fe is 0.9-0.99, and the molar ratio of (Al + Fe)/Si is 1.1-1.3.
The invention has wider optional range of the polymerization conditions, as long as the polysilicate aluminum ferric flocculant can be prepared by polymerization; preferably, the conditions of the polymerization in step (4) include: the pH value is 3.5-5, the polymerization temperature is 55-80 ℃, and the polymerization time is 1-4 h. By adopting the preferable technical scheme, the prepared flocculating agent has better coagulation effect.
More preferably, the conditions of the polymerization include: the pH value is 3.5-4.4, the polymerization temperature is 55-65 ℃, and the polymerization time is 2-4 h.
According to the invention, preferably, the polymerization is carried out with stirring at a rate of from 25 to 50rpm, more preferably from 25 to 35 rpm.
In a preferred embodiment of the present invention, the aging conditions in step (4) include: the aging time is 12-24 h.
Preferably, the aging is carried out without heating (e.g., at room temperature).
According to a preferred embodiment of the present invention, as shown in fig. 1, the method for preparing the polysilicate aluminum ferric flocculant comprises the following steps:
(1) drying and crushing the gasified slag in sequence, wherein in the crushed product, the proportion of particles with the granularity less than or equal to 80 meshes is more than 90 wt%;
mixing the gasification slag product obtained after crushing with an acid solution I with the concentration of 0.5-1mol/L to perform a first acid dissolution reaction, wherein the conditions of the first acid dissolution reaction comprise: the liquid-solid weight ratio is 2-6:1, and the first reaction time is 60-180 min;
after the first acid dissolution reaction is carried out, filtering and separating a product after the reaction to obtain a first solid product and an iron-containing filtrate, and sequentially carrying out first washing and first drying on the first solid product to obtain a washing liquid I and a filter residue I, wherein the first drying enables the water content in the filter residue I to be less than or equal to 8 wt%;
(2) mixing alkaline solids and the filter residue I according to the weight ratio of 0.1-0.3, and roasting and activating to obtain activated residue; the roasting activation conditions comprise: the roasting temperature is 600-750 ℃, and the roasting time is 60-180 min;
(3) mixing the activated slag with an acid solution II to perform a second acid dissolution reaction, wherein the conditions of the second acid dissolution reaction comprise: the liquid-solid weight ratio is 3-8:1, and the second reaction time is 60-180 min;
after the second acid dissolution reaction is carried out, separating the product after the reaction to obtain a second solid product and a filtrate containing silicon and aluminum, and sequentially carrying out second washing on the second solid product to obtain a washing liquid II and a filter residue II;
(4) contacting the iron-containing filtrate with the silicon-aluminum-containing filtrate for polymerization, wherein the dosage of the iron-containing filtrate and the dosage of the silicon-aluminum-containing filtrate meet the following requirements: the molar ratio of Al/Fe is 0.9-1.1, and the molar ratio of (Al + Fe)/Si is 0.9-1.3; the polymerization conditions include: the pH value is 3.5-5, the polymerization temperature is 55-80 ℃, and the polymerization time is 1-4 h;
then aging at room temperature for 12-24h to obtain a polysilicate aluminum ferric flocculant;
the washing solution I and the washing solution II generated in the process are used for preparing the acid solution I and the acid solution II.
The apparatus for the acid dissolution reaction or polymerization reaction is not limited in the present invention, and may be any existing apparatus capable of performing the above acid dissolution reaction or polymerization reaction, and may be, for example, a reactor with a tetrafluoroethylene liner.
The polysilicate aluminum ferric flocculant prepared by the method integrates the characteristics of large floc and quick sedimentation of aluminum salt and ferric salt flocculants and the bridging adsorption effect of the polysilicate flocculant, and has good coagulation effect and stability.
The invention provides a polysilicate aluminum ferric flocculant prepared by the method of the first aspect.
The third aspect of the invention provides an application of the polysilicate aluminum ferric flocculant in the second aspect in treating coal chemical industry wastewater, mine water or gasified black water.
In the invention, the gasified black water refers to water containing a large amount of gasified fine slag after flash evaporation in the gasification process, and is known in the art and is not described herein again.
The polysilicate aluminum ferric flocculant is used for treating coal chemical industry wastewater, mine water or gasified black water, and a person skilled in the art can treat the treated coal chemical industry wastewater, mine water or gasified black water again according to actual requirements or directly use the treated coal chemical industry wastewater, mine water or gasified black water as process water for a humidifying tower in a flash evaporation section and a synthetic gas washing tower in a gasification section, which is not limited by the invention.
The present invention will be described in detail below by way of examples. In the following examples, the raw materials involved are commercial products, unless otherwise indicated, wherein the gasification slag: the gasified slag I, the gasified slag II and the gasified slag III (the compositions are shown in the table 1) are all from Ningxia coal industry, the national energy group, but the company has a limited responsibility.
In the following examples, the ash content of the gasified slag was determined by X-ray fluorescence spectroscopy (XRF); the carbon residue content of the gasified slag is obtained by testing through an industrial analyzer.
In the following examples, the room temperature refers to 20 ℃. + -. 5 ℃.
Example 1
This example illustrates the process and polysilicate aluminum ferric flocculant of the present invention.
(1) Drying, grinding and crushing the gasified slag I in sequence, wherein in the crushed product, the proportion of particles with the granularity of less than or equal to 80 meshes is 90 wt%;
adding a gasification slag product obtained after crushing and a hydrochloric acid solution I with the concentration of 0.8mol/L into a reactor with a tetrafluoroethylene liner for mixing, and carrying out a first acid dissolution reaction under the stirring of 30rpm, wherein the conditions of the first acid dissolution reaction are as follows: the liquid-solid weight ratio is 4:1, and the first reaction time is 80 min;
after the first acid dissolution reaction is carried out, filtering and separating a product after the reaction to obtain a first solid product and an iron-containing filtrate, and sequentially carrying out first washing and first drying on the first solid product to obtain a washing liquid I and a filter residue I, wherein the first drying enables the water content in the filter residue I to be less than 8 wt%;
the washing solution I is used for preparing a hydrochloric acid solution I;
(2) mixing sodium hydroxide solid and the filter residue I according to the weight ratio of 0.2, and roasting at 700 ℃ for 60min for activation to obtain activated residue;
(3) adding the activated slag and 1mol/L hydrochloric acid solution II into a reactor with a tetrafluoroethylene liner in a liquid-solid weight ratio of 4:1, mixing, and carrying out a second acid solution reaction for 100min under stirring at 40 rpm;
after the second acid dissolution reaction is carried out, filtering and separating the product after the reaction to obtain a second solid product and a filtrate containing silicon and aluminum, and sequentially carrying out second washing on the second solid product without drying to obtain a washing liquid II and a filter residue II; the washing solution II is used for preparing a hydrochloric acid solution II;
(4) mixing the iron-containing filtrate and the silicon-containing aluminum filtrate, and carrying out polymerization under stirring of 60rpm, wherein the iron-containing filtrate and the silicon-containing aluminum filtrate are used in the following amounts: the molar ratio of Al/Fe is 0.9, and the molar ratio of (Al + Fe)/Si is 1.1; the polymerization conditions are as follows: the pH value is 3.5, the polymerization temperature is 58 ℃, and the polymerization time is 2 h;
and then aging for 24 hours at room temperature to obtain the polysilicate aluminum ferric flocculant.
Comparative example 1
The process is carried out as in example 1, except that in step (2) a sodium hydroxide solution having a concentration of 1mol/L is used instead of the sodium hydroxide solid, the sodium hydroxide solution in terms of sodium hydroxide is mixed with the residue I in a weight ratio of 0.2, and the mixture is heated and stirred at 90 ℃ for reaction for 180min to obtain an alkali solution and an alkaline residue filter cake, which is used in step (3) to be mixed with the hydrochloric acid solution II for the second acidolysis reaction and is carried out according to the process parameters shown in Table 2, otherwise the process is the same as in example 1.
Examples 2 to 4
The procedure is as in example 1, except that the process parameters shown in Table 2 are used, otherwise the same as in example 1.
Examples 5 to 7
The procedure is as in example 1, except that the process parameters shown in Table 2 are used, otherwise the same as in example 1.
Example 8
The procedure of example 1 was repeated, except that the gasified slag II shown in Table 1 was used, and the procedure was otherwise the same as in example 1.
Example 9
The procedure of example 1 was repeated, except that the gasified slag III shown in Table 1 was used, and the procedure was otherwise the same as in example 1.
TABLE 1
TABLE 2
Test example 1
The polyaluminum ferric silicate flocculants prepared in the above examples 1 to 9 and comparative example 1 were used for the performance test of the treated gasified black water, respectively. The gasified black water is taken from a vacuum flash tank of a gasification plant of Ningxia coal industry, Limited liability company of national energy group, coal oil content company to an inlet pipeline of the clarifying tank, and the solid content of the gasified black water is 5000 mg/L.
Measuring 20ml of corresponding flocculant, adding 1L of the simulated gasified black water under the stirring condition of 100rpm, stirring for 1min, and standing for 5 min; the supernatant was then taken to determine the suspended matter content (ss), and the results are shown in Table 3.
TABLE 3
| Flocculating agent | Suspended matter content (ss), mg/L |
| Example 1 | 436 |
| Comparative example 1 | 1380 |
| Example 2 | 498 |
| Example 3 | 375 |
| Example 4 | 536 |
| Example 5 | 551 |
| Example 6 | 574 |
| Example 7 | 1270 |
| Example 8 | 419 |
| Example 9 | 1350 |
As can be seen from the results in tables 2 and 3, the polysilicate aluminum ferric flocculant prepared by the embodiment of the method of the invention can be used for the primary treatment of gasified black water, and has good flocculation effect.
It can be seen from the comparison of examples 1, 8 and 9 that the technical effect is better by adopting the technical solution of the present invention for gasification of slag satisfying specific conditions.
As is clear from comparative example 1 and examples 5 to 7, by adopting the preferred embodiment of the present invention containing specific parameters, particularly, the weight ratio of caustic sludge, the molar ratio of Al/Fe, (Al + Fe)/Si, the polymerization temperature and the polymerization time in specific ranges, a more excellent technical effect can be obtained.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for preparing a polysilicate aluminum ferric flocculant is characterized by comprising the following steps:
(1) mixing the gasified residue with an acid solution I, and carrying out a first acid dissolution reaction to obtain an iron-containing filtrate and a filter residue I;
(2) mixing the filter residue I with alkaline solids, and roasting and activating to obtain activated slag;
(3) mixing the activated slag with an acid solution II, and carrying out a second acid dissolution reaction to obtain a silicon-aluminum-containing filtrate and a filter residue II;
(4) contacting the iron-containing filtrate with the silicon-aluminum-containing filtrate, polymerizing, and then aging to obtain a polysilicate aluminum ferric flocculant;
optionally, the method further comprises: after the first acid dissolution reaction is carried out, separating the product after the reaction to obtain a first solid product and the iron-containing filtrate, and carrying out first washing on the first solid product to obtain washing liquid I;
optionally, the method further comprises: after the second acid solution reaction is carried out, separating the product after the reaction to obtain a second solid product and the filtrate containing silicon and aluminum, and carrying out second washing on the second solid product to obtain a washing liquid II.
2. The method of claim 1, wherein the gasified slag satisfies: ash component containing SiO2、Al2O3And Fe2O3And SiO2The content is more than or equal to 48 wt%, and Al2O3The content is more than or equal to 18 wt%, Fe2O3The content is more than or equal to 7wt percent, and the carbon residue content of the gasified slag is less than or equal to 3 percent;
preferably, the gasification slag satisfies: ash component containing SiO2、Al2O3And Fe2O3And SiO2The content is more than or equal to 50 wt%, Al2O3The content is more than or equal to 18 wt%, Fe2O3The content is more than or equal to 10 wt%, and the gasified slagThe content of carbon residue is less than or equal to 3 percent;
preferably, the liquid-solid weight ratio of the first acid dissolution reaction in step (1) is 2-6:1, more preferably 2-4: 1;
preferably, the concentration of the acid solution I in the step (1) is 0.5-1 mol/L;
preferably, the conditions of the first acid dissolution reaction include: the first reaction time is 60-180min, more preferably 60-120 min;
preferably, the first acid dissolution reaction is carried out under stirring at a rate of 20-100rpm, more preferably 20-40 rpm.
3. The method of claim 1 or 2, wherein step (1) further comprises: optionally drying and crushing the gasified slag in sequence before the mixing;
preferably, in the product obtained after crushing, the proportion of particles with the particle size less than or equal to 80 meshes is more than 90 wt%;
preferably, step (1) further comprises: carrying out first drying on a first solid product obtained after the first washing to obtain filter residue I;
preferably, the first drying makes the moisture content in the filter residue I less than or equal to 8 wt%;
preferably, the detergent used in the first washing is water.
4. A process according to any one of claims 1 to 3, wherein the weight ratio of the basic solid to the residue i in step (2) is between 0.1 and 0.3;
preferably, the weight ratio of the alkaline solid to the filter residue I is 0.17-0.3;
preferably, the basic solid is a basic sodium-containing compound and/or a basic potassium-containing compound, more preferably a basic sodium-containing compound;
further preferably, the basic sodium-containing compound is selected from sodium hydroxide and/or sodium carbonate, more preferably sodium hydroxide;
preferably, the conditions of the calcination activation include: the roasting temperature is 600-750 ℃, and the roasting time is 60-180min, more preferably 60-120 min.
5. The process according to any one of claims 1 to 4, wherein the liquid-to-solid weight ratio in the second acid-dissolving reaction in step (3) is 3-8:1, more preferably 3-6: 1;
preferably, the concentration of the acid solution II in the step (3) is 0.8-1.3 mol/L;
preferably, the conditions of the second acid solution reaction in step (3) include: the second reaction time is 60-180min, more preferably 60-120 min;
preferably, the second acid dissolution reaction is carried out under stirring at a rate of 20 to 100rpm, more preferably 20 to 40 rpm;
preferably, the detergent used in the second washing is water.
6. The process according to any one of claims 1 to 5, wherein the acid solution I and the acid solution II are each independently selected from a hydrochloric acid solution and/or a sulfuric acid solution;
preferably, the acid solution I and the acid solution II are respectively and independently selected from at least one of fresh acid, waste acid for production and a solution prepared from acid and a washing liquid, and the washing liquid is the washing liquid I and/or the washing liquid II.
7. The method of any one of claims 1 to 6, wherein the iron-containing filtrate and the silicon-containing aluminum filtrate in step (4) are used in amounts such that: the molar ratio of Al/Fe is 0.9-1.1, and the molar ratio of (Al + Fe)/Si is 0.9-1.3;
preferably, the iron-containing filtrate and the silicon-aluminum-containing filtrate are used in amounts that satisfy: the molar ratio of Al/Fe is 0.9-0.99, and the molar ratio of (Al + Fe)/Si is 1.1-1.3.
8. The process of any one of claims 1-7, wherein the conditions of the polymerization in step (4) comprise: the pH value is 3.5-5, the polymerization temperature is 55-80 ℃, and the polymerization time is 1-4 h;
preferably, the conditions of the polymerization include: the pH value is 3.5-4.4, the polymerization temperature is 55-65 ℃, and the polymerization time is 2-4 h;
preferably, the polymerization is carried out with stirring at a rate of from 25 to 50rpm, more preferably from 25 to 35 rpm;
preferably, the aging conditions in step (4) include: the aging time is 12-24 h;
preferably, the aging is carried out without heating.
9. The polyaluminum ferric silicate flocculant prepared by the method of any one of claims 1 to 8.
10. The use of the polyaluminum ferric silicate flocculant of claim 9 for treating coal chemical wastewater, mine water or gasified black water.
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