CN111232997A - Method for co-producing analcime by high-modulus water glass and product thereof - Google Patents
Method for co-producing analcime by high-modulus water glass and product thereof Download PDFInfo
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- CN111232997A CN111232997A CN201811446656.0A CN201811446656A CN111232997A CN 111232997 A CN111232997 A CN 111232997A CN 201811446656 A CN201811446656 A CN 201811446656A CN 111232997 A CN111232997 A CN 111232997A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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Abstract
The invention relates to the field of utilization of silicon and aluminum mineral residues, and discloses a method for co-producing analcime by high-modulus water glass, which is characterized by comprising the following steps of: I) mixing the low-modulus water glass solution with the silica slag to perform hydrothermal reaction, and then performing solid-liquid separation to obtain a high-modulus water glass solution and filter residues; II) washing and drying the filter residue to obtain analcime; wherein SiO in the silicon slag2Is 50-80 wt%, Al2O3Is contained in an amount of 10 to 20% by weight. The water glass prepared by the method has high modulus and Na in the water glass2The O content can meet the requirement of industrial liquid sodium silicate, and the analcime is prepared, so that the silicon slag is fully utilized, and the resource utilization rate is integrally improved.
Description
Technical Field
The invention relates to the field of utilization of silicon and aluminum mineral residues, in particular to a method for co-producing analcime by high-modulus water glass, a method for preparing high-modulus water glass co-producing analcime by silica slag or high-alumina fly ash and a product thereof.
Background
The solid residue after the aluminum extraction of fly ash, coal gangue and kaolin which are mainly stockpiled causes serious pollution to the surrounding environment and greater potential safety hazard for burying, but the solid residue still contains rich silicon and aluminum components, and SiO in the residue is common2About 50-80% of Al2O3The content is about 5-20%, and the solid residues are completely recycled, so that the environmental hazard caused by the solid residues can be solved, and the economic benefit and the social benefit of the comprehensive utilization of the fly ash, the coal gangue and the kaolin can be improved.
The water glass is the water solution of sodium silicate, and is a chemical product with wide application. The production method of the water glass is divided into a solid phase method and a liquid phase method; the solid phase method is to mix quartz sand and soda ash according to a certain proportion and then melt the mixture at high temperature to generate molten solid sodium silicate, the water glass produced by the solid phase method can be used for preparing water glass with high modulus, but the energy consumption is large, the water glass produced by the liquid phase method is to react sodium hydroxide solution and quartz powder in a reaction kettle to generate sodium silicate solution, and then the sodium silicate solution is filtered to obtain a water glass product, the energy consumption is low, but the modulus of the water glass is lower.
Zeolite is aluminosilicate with developed pore structure, has excellent ion exchange performance, adsorption performance, catalytic performance and the like, and is widely applied to the chemical fields of water treatment, gas drying and the like. The analcime is aluminum-containing sodium aluminosilicate with a structural formula of [ Na (Si)2Al)06·H2O]. Most analcime has a fixed chemical composition with only a small amount of potassium or calcium substituted for sodium and a portion of aluminum substituted for silicon. Analcime on metal ion adsorption sieveAnd the method has great market potential value in the aspects of separation, gas separation and pure water separation. The analcime shows unique molecular sieve characteristics after being chemically modified, has good adsorption effect on heavy metal ions such as Pb, Cu, Zn and the like, and can be used for treating wastewater containing the heavy metals.
In the preparation process of the traditional analcime molecular sieve, basically, medicines and reagents with higher chemical purity are used, and low-purity raw materials with low price are rarely used. The high-alumina fly ash in China has huge yield and the main component of the high-alumina fly ash is SiO2And Al2O3In the engineering, the silica slag is produced after the high-alumina fly ash is subjected to aluminum extraction by an acid method, and is used as a filling foundation in general, however, the consumption of the silica slag is still lower than the huge discharge amount, and a large amount of silica slag can only be stacked and left unused, so that precious land resources are occupied, and the environment can be polluted. SiO still contained in the silicon slag2And Al2O3Can be used as raw materials for producing water glass and analcime. At present, common fly ash is mostly used for producing water glass or analcite, the produced water glass has low modulus, and the production of high modulus water glass mostly needs a calcination process, the process is complex, and the energy consumption is higher.
Disclosure of Invention
The invention aims to solve the problems of complex process, high energy consumption and low modulus of produced water glass in the prior art of producing the water glass by using fly ash, and provides a method for preparing the high-modulus water glass and coproducing analcime by using silica slag, and the high-modulus water glass and analcime product prepared by using the method. The method has the advantages of simple operation process, low energy consumption, high modulus of the prepared water glass, and Na in the water glass2The content of O can meet the standard of industrial liquid water glass (GB/T4209-2008 industrial sodium silicate), and the analcite is prepared, so that the silicon slag residue is fully utilized, and the resource utilization rate is integrally improved.
In order to achieve the above object, a first aspect of the present invention provides a method for co-producing analcime from high modulus water glass, which is characterized in that the method comprises the following steps:
I) mixing the low-modulus water glass solution with the silica slag to perform hydrothermal reaction, and then performing solid-liquid separation to obtain a high-modulus water glass solution and filter residues;
II) washing and drying the filter residue to obtain analcime;
wherein SiO in the silicon slag2Is 50-80 wt%, Al2O3Is contained in an amount of 5 to 20% by weight.
Preferably, in the step I), the hydrothermal reaction temperature is 120-.
Preferably, SiO in the silicon slag2In an amount of 70-80 wt.%, Al2O3The content of (B) is 8-15 wt%.
Preferably, the silica residue is selected from at least one of fly ash, coal gangue and silica residue obtained after aluminum extraction from kaolinite.
Preferably, the silicon slag contains SiO with amorphous phase2。
Preferably, in the step I), the mass ratio of the low-modulus water glass to the silica slag is 1: (2.5-5.0).
The invention provides a method for preparing high-modulus water glass and coproducing analcite from silica slag, which is characterized by comprising the following steps:
1) mixing the silicon slag with a sodium hydroxide solution to prepare mixed slurry;
2) carrying out desiliconization reaction on the slurry, and then carrying out solid-liquid separation to obtain a low-modulus water glass solution and first filter residue;
3) preparing the low-modulus water glass solution into a high-modulus water glass solution and analcime by the method for co-producing analcime by using the high-modulus water glass;
wherein SiO in the silicon slag2Is 50-80 wt%, Al2O3Is contained in an amount of 5 to 20% by weight.
Preferably, in the step 1), the mass ratio of the silicon slag to the sodium hydroxide solution is 1: (3-6), wherein the mass concentration of the sodium hydroxide solution is 10% -20%.
Preferably, in the step 2), the desiliconization reaction temperature is 60-120 ℃, and the desiliconization reaction time is 0.5-2 h;
the third aspect of the invention provides a method for preparing high-modulus water glass and coproducing analcite by using high-alumina fly ash, which is characterized by comprising the following steps:
a) contacting the high-alumina fly ash with an acid solution to carry out acid process aluminum extraction to prepare alumina and silica slag;
b) the silica slag is used for preparing the high-modulus water glass coproduction analcime by the method for preparing the high-modulus water glass coproduction analcime from the silica slag.
In a fourth aspect, the invention provides high modulus water glass and analcime prepared by the method of the invention.
By the technical scheme, the invention realizes the preparation of high-modulus water glass coproduction analcite from the silica slag, realizes the full utilization of the silica slag, achieves the utilization rate of 100 percent, and simultaneously provides a simple process for the coproduction of the high-modulus water glass and the analcite, the modulus of the prepared high-modulus water glass reaches 3.5, and Na in the water glass2The content of O can meet the standard of industrial liquid water glass, and the prepared analcime has the granularity of 4-10 mu m and can meet the requirement of the particle size of various analcime applications.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a schematic flow chart of the process for preparing high-modulus water glass and coproducing analcite from silica slag;
FIG. 2 is an XRD spectrum of a analcime prepared according to example 6 of the present invention;
FIG. 3 is an SEM image of a analcime prepared in example 6 of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the description herein of specific embodiments is only for purposes of illustration and understanding and is not intended to limit the invention.
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.
The invention provides a method for co-producing analcime by high-modulus water glass, which is characterized by comprising the following steps:
I) mixing the low-modulus water glass solution with the silica slag to perform hydrothermal reaction, and then performing solid-liquid separation to obtain a high-modulus water glass solution and filter residues;
II) washing and drying the filter residue to obtain analcime;
wherein SiO in the silicon slag2Is 50-80 wt%, Al2O3Is contained in an amount of 5 to 20% by weight.
Preferably, SiO in the silicon slag2In an amount of 70-80 wt.%, Al2O3The content of (B) is 8-15 wt%.
Preferably, the residue satisfying the above silicon and aluminum contents may be at least one selected from fly ash, coal gangue and silica residue obtained after aluminum extraction from kaolin.
According to the invention, the silicon slag preferably contains SiO with amorphous phase2. Wherein the amorphous SiO2Means that SiO in the present invention2Mainly using SiO with amorphous phase2Are present.
In the invention, the modulus of the low-modulus water glass in the step I) is preferably 0.5-1.5, and the low-modulus water glass can be prepared by the method of the invention and can also be obtained commercially.
In the invention, the high-modulus water glass is prepared by a hydrothermal reaction, in the step I), the hydrothermal reaction temperature can be 120-200 ℃, the hydrothermal reaction time can be 1-6h, and the hydrothermal reaction pressure can be 0.2-2.0 MPa; in order to further increase the modulus of the prepared high-modulus water glass, preferably, the hydrothermal reaction temperature can be 150-180 ℃, the hydrothermal reaction time can be 2.5-5h, and the hydrothermal reaction pressure can be 0.8-1.3 MPa.
Preferably, in the step I), the mass ratio of the low-modulus water glass to the silica slag is 1: (2.5-5.0).
Specifically, the hydrothermal reaction process may be that the mass ratio of the low-modulus water glass prepared by the method of the present invention to the silica slag is 1: (2.5-5.0), then putting the mixture into a hydrothermal reaction kettle, controlling the reaction temperature to be 120-200 ℃ and the reaction pressure to be 0.2-2.0MPa by steam heating, continuously reacting for 1-6h, taking out the slurry after the reaction is finished, and filtering to obtain a filtrate and second filter residue, wherein the filtrate is high-modulus water glass with the modulus of 2.5-3.5, and the modulus of the high-modulus water glass and Na2The content of O is determined according to GB/T4209-2008 industrial sodium silicate; and washing and drying the second filter residue to obtain the analcime with the granularity of 4-10 mu m.
Specifically, the washing process can adopt water with the temperature of 50-100 ℃ for washing for 2-6 times, wherein the using amount of the water is 3-6 times of the weight of the filter residue formed by filtering; the drying process can adopt drying at 80-100 ℃ for 3-10 h.
The invention provides a method for preparing high-modulus water glass and coproducing analcite from silica slag, which is characterized by comprising the following steps:
1) mixing the silicon slag with a sodium hydroxide solution to prepare mixed slurry;
2) carrying out desiliconization reaction on the slurry, and then carrying out solid-liquid separation to obtain a low-modulus water glass solution and first filter residue;
3) preparing the low-modulus water glass solution into a high-modulus water glass solution and analcime by the method for co-producing analcime by using the high-modulus water glass;
wherein SiO in the silicon slag2Is 50-80 wt%, Al2O3Is contained in an amount of 5 to 20% by weight.
Preferably, SiO in the silicon slag2In an amount of 70-80 wt.%, Al2O3The content of (B) is 8-15 wt%.
According to the invention, in order to prepare the low-modulus water glass, preferably, in the step 1), the mass ratio of the silicon slag to the sodium hydroxide solution is 1: (3-6), wherein the mass concentration of the sodium hydroxide solution is 10% -20%.
According to the invention, in order to prepare the low-modulus water glass, preferably, in the step 2), the desiliconization reaction temperature is 60-120 ℃, and the desiliconization reaction time is 0.5-2 h;
specifically, the desilication reaction process may be that the silicon slag and the sodium hydroxide solution are mixed according to a mass ratio of 1: (3-6) uniformly mixing, wherein the mass concentration of the sodium hydroxide solution is 10% -20%, then putting the uniformly mixed slurry into a desilication reaction kettle, heating by steam to control the reaction temperature to be 60-120 ℃, continuously reacting for 0.5-2h, taking out the slurry after the reaction is finished, and filtering to obtain a filtrate and first filter residue, wherein the filtrate is the low-modulus water glass with the modulus of 0.5-1.5, and the modulus of the low-modulus water glass is determined according to sodium silicate in GB/T4209-2008 industrial.
According to the invention, the water glass prepared by the method is low-modulus water glass, the modulus of the water glass is 0.5-1.5, and the water glass can be further used for preparing high-modulus water glass.
The third aspect of the invention provides a method for preparing high-modulus water glass and coproducing analcite by using high-alumina fly ash, which is characterized by comprising the following steps:
a) contacting the high-alumina fly ash with an acid solution to carry out acid process aluminum extraction to prepare alumina and silica slag;
b) the silica slag is used for preparing the high-modulus water glass coproduction analcime by the method for preparing the high-modulus water glass coproduction analcime from the silica slag.
According to a preferred embodiment of the invention, the silica slag can be derived from residue of acid-process aluminum extraction of high-alumina fly ash, wherein the acid-process aluminum extraction process can be that high-alumina fly ash is subjected to acid dissolution to extract alumina by using sulfuric acid or hydrochloric acid, and SiO of the silica slag is subjected to acid leaching2The activity is very high. In order to improve the extraction efficiency of the alumina, hydrochloric acid is preferably adopted to extract the high-alumina fly ashAlumina of (2). Specifically, the preparation process of the silica slag can be that firstly, the high-alumina fly ash is ground by a grinding grinder, the particle size range of the ground particles is 100-200 meshes, water is added to prepare slurry with the solid content of 25-35%, a vertical ring magnetic separator is used for magnetic separation for 2-4 times under the condition that the magnetic field intensity is 1.2-1.8 ten thousand GS, and filter cakes with the solid content of 35-45 wt% are obtained after filter pressing by a plate and frame filter press; adding hydrochloric acid with the concentration of 20-26 wt% into the filter cake to carry out acid dissolution reaction, wherein the molar ratio of HCl in the hydrochloric acid to alumina in the high-alumina fly ash is 2.5-3.5:1, the reaction temperature is 100 ℃ and 180 ℃, the reaction pressure is 0.3-1.0MPa, after the reaction time is 1.2-3h, carrying out suction filtration, washing the filter cake with water with the solid-liquid ratio of the high-alumina fly ash to the water being 0.5-2:1, and filtering to obtain the silica slag.
Wherein the high-alumina fly ash comes from wet fly ash discharged from a certain power plant in inner Mongolia and comprises Al as a main component2O352% by weight of SiO237% by weight.
The method for preparing high-modulus water glass and coproducing analcite by using high-alumina fly ash can improve the utilization efficiency of the high-alumina fly ash. Wherein, the step a) can produce alumina, and the generated silica slag can utilize the step b) to prepare high-modulus water glass and coproduce analcite.
In a fourth aspect, the invention provides high modulus water glass and analcime prepared by the method of the invention.
The present invention will be described in detail below by way of examples.
In the following examples, the modulus of water glass is determined by GB/T4209-2008 sodium silicate industries; measuring the analcime particle size by using a laser particle size analyzer;
the high-alumina fly ash comes from wet fly ash discharged from inner Mongolia power plants and comprises Al as a main component2O352% by weight of SiO237 wt%;
coal gangue is collected from inner Mongolia region and mainly contains Al2O331% by weight of SiO 260% by weight;
kaolinite is collected from inner Mongolia region of stone and contains Al as main component2O337% by weight of SiO242 wt%;
the main phase composition in the prepared analcime is determined by XRD;
observing the morphological characteristics of the prepared analcime through SEM;
in the following examples, the yield of water glass was calculated as follows: (SiO in Water glass)2Weight percent multiplied by water glass volume multiplied by density)/(silicon slag weight multiplied by silicon slag SiO2Weight%).
Preparation example 1
Grinding the high-alumina fly ash by a grinding grinder, wherein the particle size range of the ground particles is 100-200 meshes, adding water to prepare slurry with the solid content of 30 weight percent, magnetically separating for 3 times by using a vertical ring magnetic separator under the condition that the magnetic field intensity is 1.5 ten thousand GS, and performing filter pressing by a plate-and-frame filter press to obtain a filter cake with the solid content of 42 weight percent; adding hydrochloric acid with the concentration of 31 weight percent into the filter cake to perform acid dissolution reaction, wherein the molar ratio of HCl in the hydrochloric acid to alumina in the high-alumina fly ash is 3: 1, carrying out suction filtration after the reaction temperature is 150 ℃, the reaction pressure is 0.7MPa and the reaction time is 1.8h, wherein the solid-to-liquid ratio of the high-alumina fly ash to water for a filter cake is 1.3: 1, washing with water, and filtering to obtain silica residue.
SiO in the prepared silicon slag2Is 70 wt% of Al2O3The content of (B) is 15% by weight.
Preparation example 2
Crushing coal gangue into particles with the particle size of 5-10mm, activating the coal gangue particles by adopting a rotary kiln, wherein the activation temperature is 850 ℃, grinding the activated coal gangue particles by adopting a grinding grinder, the particle size range of the ground particles is 100-200 meshes, adding water to prepare slurry with the solid content of 30 weight percent, carrying out magnetic separation for 3 times by using a vertical ring magnetic separator under the magnetic field intensity of 1.5 ten thousand GS, and carrying out filter pressing by using a plate-and-frame filter press to obtain a filter cake with the solid content of 42 weight percent; adding hydrochloric acid with the concentration of 26 weight percent into the filter cake to carry out acid dissolution reaction, wherein the molar ratio of HCl in the hydrochloric acid to alumina in the coal gangue is 3: 1, carrying out suction filtration after the reaction temperature is 140 ℃, the reaction pressure is 0.6MPa and the reaction time is 1.5h, wherein the solid-to-liquid ratio of the high-alumina fly ash to water for a filter cake is 1.3: 1, washing with water, and filtering to obtain silica residue.
SiO in the prepared silicon slag2Is 76% by weight, Al2O3The content of (B) is 9% by weight.
Preparation example 3
Crushing kaolinite into particles with the particle size of 5-10mm, activating the coal gangue particles by adopting a rotary kiln, wherein the activation temperature is 900 ℃, the activated coal gangue particles are ground by adopting a grinding grinder, the particle size range of the ground particles is 200 meshes, hydrochloric acid with the concentration of 28 weight percent is added into the kaolinite crushed particles for carrying out acid dissolution reaction, and the molar ratio of HCl in hydrochloric acid to alumina in the kaolinite is 3: 1, carrying out suction filtration after the reaction temperature is 150 ℃, the reaction pressure is 0.7MPa and the reaction time is 1.5h, wherein the solid-to-liquid ratio of the high-alumina fly ash to water for a filter cake is 1.3: 1, washing with water, and filtering to obtain silica residue.
SiO in the prepared silicon slag2Is 80 wt% of Al2O3The content of (B) is 8% by weight.
Examples 1-5 illustrate the preparation of low modulus waterglass.
Example 1
Mixing the silicon slag obtained in the preparation example 1 with a sodium hydroxide solution with the mass concentration of 15% according to a mass ratio of 1: 4.5, uniformly mixing to obtain mixed slurry, then putting the mixed slurry into a desilication reaction kettle, heating by steam to control the reaction temperature, so that the slurry reacts for 1.2h at 100 ℃, taking out the slurry after the reaction is finished, filtering to obtain filtrate, namely the low-modulus water glass, wherein the modulus of the prepared water glass is 1.1 according to GB/T4209-2008 industrial sodium silicate.
Example 2
Mixing the silicon slag obtained in the preparation example 1 with a sodium hydroxide solution with the mass concentration of 10% according to the mass ratio of 1: 3, uniformly mixing to prepare mixed slurry, then putting the mixed slurry into a desilication reaction kettle, heating by steam to control the reaction temperature, so that the slurry reacts at 60 ℃ for 2 hours, taking out the slurry after the reaction is finished, and filtering to obtain filtrate, namely the low-modulus water glass, wherein the modulus of the prepared water glass is 0.9 measured according to GB/T4209-2008 industrial sodium silicate.
Example 3
Mixing the silicon slag obtained in the preparation example 1 with a sodium hydroxide solution with the mass concentration of 20% according to the mass ratio of 1: 6, uniformly mixing to obtain mixed slurry, then putting the mixed slurry into a desilication reaction kettle, heating by steam to control the reaction temperature, so that the slurry reacts at 120 ℃ for 0.5h, taking out the slurry after the reaction is finished, and filtering to obtain filtrate, namely the low-modulus water glass, wherein the modulus of the prepared water glass is 1.5 measured according to GB/T4209-2008 industrial sodium silicate.
Example 4
The process of example 1 was followed except that: the silica fume obtained in preparation example 2 is used for preparing low-modulus water glass, and the modulus of the prepared water glass measured according to GB/T4209-2008 industrial sodium silicate is 1.2.
Example 5
The process of example 1 was followed except that: the silica fume obtained in preparation example 3, low modulus water glass, was used, and the modulus of the water glass measured in GB/T4209-2008 sodium silicate industry, was 1.4.
Comparative example 1
The method of the embodiment 1 is characterized in that the mass ratio of the silicon slag to the sodium hydroxide is 2:1, the slurry is too viscous, the reaction efficiency is low, and the modulus of the water glass obtained by filtering is only 0.4.
Examples 6-14 illustrate the preparation of high modulus water glass and analcime.
Example 6
Mixing the low-modulus water glass obtained in the example 1 and the silicon slag obtained in the preparation example 1 according to the mass ratio of 1: 3, uniformly mixing, then putting into a hydrothermal reaction kettle, continuously reacting for 5 hours at the reaction temperature of 150 ℃ and the reaction pressure of 1.3MPa by steam heating, taking out slurry after the reaction is finished, and filtering to obtain filtrate, namely the high-modulus water glass. The modulus of the produced water glass and Na in the water glass are measured according to GB/T4209-2008 industrial sodium silicate2O content, results are shown in Table 1;
washing the filter residue with 80 deg.C water for 4 times, wherein the amount of water is 4.5 times of the weight of the filter residue, washing, and drying at 90 deg.C for 7 hr to obtain analcime. The particle size of the analcime produced was measured using a laser particle sizer and the results are given in table 1.
Example 7
Mixing the low-modulus water glass obtained in the example 2 and the silicon slag obtained in the preparation example 1 according to the mass ratio of 1: 4, uniformly mixing, then putting into a hydrothermal reaction kettle, continuously reacting for 2.5 hours at the reaction temperature of 180 ℃ and the reaction pressure of 0.8MPa by steam heating, taking out slurry after the reaction is finished, and filtering to obtain filtrate, namely the high-modulus water glass. The modulus of the produced water glass and Na in the water glass are measured according to GB/T4209-2008 industrial sodium silicate2O content, results are shown in Table 1;
washing the filter residue with 60 deg.C water for 3 times, wherein the water amount is 3 times of the weight of the filter residue formed by filtration, washing, and drying at 100 deg.C for 5 hr to obtain analcime. The particle size of the analcime produced was measured using a laser particle sizer and the results are given in table 1.
Example 8
Mixing the low-modulus water glass obtained in the example 3 and the silicon slag obtained in the preparation example 1 according to the mass ratio of 1: 5, uniformly mixing, then putting into a hydrothermal reaction kettle, continuously reacting for 3.5 hours at the reaction temperature of 165 ℃ and the reaction pressure of 1.1MPa by steam heating, taking out slurry after the reaction is finished, and filtering to obtain filtrate, namely the high-modulus water glass. The modulus of the produced water glass and Na in the water glass are measured according to GB/T4209-2008 industrial sodium silicate2O content, results are shown in Table 1;
washing the filter residue with 100 deg.C water for 2 times, wherein the amount of water is 5 times of the weight of the filter residue formed by filtration, washing, and drying at 80 deg.C for 9 hr to obtain analcime. The particle size of the analcime produced was measured using a laser particle sizer and the results are given in table 1.
Example 9
The process of example 6 was followed except that: in the hydrothermal reaction kettle, the reaction temperature is controlled to be 120 ℃ through steam heating, the reaction pressure is 2.0MPa, and the reaction is continued for 6 hours. The results are shown in Table 1.
Example 10
The process of example 6 was followed except that: in the hydrothermal reaction kettle, the reaction temperature is controlled to be 200 ℃ through steam heating, the reaction pressure is 0.2MPa, and the reaction is continued for 1.2 h. The results are shown in Table 1.
Example 11
The procedure of example 6 was followed except that the low modulus water glass was obtained commercially with a modulus of 1.2. The results are shown in Table 1.
Example 12
The process of example 6 was followed except that: mixing the low-modulus water glass obtained in the example 1 and the silicon slag obtained in the preparation example 1 according to the mass ratio of 1: 6.5, mixing evenly, and then putting into a hydrothermal reaction kettle. The results are shown in Table 1.
Example 13
The process of example 6 was followed except that: mixing the low-modulus water glass obtained in the example 1 and the silicon slag obtained in the preparation example 1 according to the mass ratio of 1: 1.2, and then the mixture is put into a hydrothermal reaction kettle. The results are shown in Table 1.
Example 14
Following the procedure of example 6: except that the low-modulus water glass obtained in the example 4 and the silicon slag obtained in the preparation example 2 are mixed according to the mass ratio of 1: 3, uniformly mixing. The results are shown in Table 1.
Example 15
Following the procedure of example 6: except that the low-modulus water glass obtained in the example 5 and the silicon slag obtained in the preparation example 3 are mixed according to the mass ratio of 1: 3, uniformly mixing. The results are shown in Table 1.
Comparative example 2
Mixing the silicon slag obtained in the preparation example 1 with a sodium hydroxide solution with the mass concentration of 15% according to a mass ratio of 1: 4.5, uniformly mixing to obtain mixed slurry, then putting the mixed slurry into a desilication reaction kettle, controlling the reaction temperature through steam heating to enable the slurry to react for 1.2h at 100 ℃, after the reaction is finished, putting all the slurry into a hydrothermal reaction kettle, continuously reacting for 5h at 150 ℃ through steam heating to control the reaction temperature and 1.3MPa, after the reaction is finished, taking out the slurry, filtering, and measuring the modulus of the prepared water glass according to GB/T4209-2008 industrial sodium silicate, wherein the result is shown in Table 1;
washing the filter residue with 80 deg.C water for 4 times, wherein the amount of water is 4.5 times of the weight of the filter residue, washing, and drying at 90 deg.C for 7 hr to obtain analcime. The particle size of the analcime produced was measured using a laser particle sizer and the results are given in table 1.
Comparative example 3
Mixing common fly ash (Al)2O331% by weight of SiO262 weight percent) and a sodium hydroxide solution with the mass concentration of 15 percent according to the mass ratio of 1: 4, uniformly mixing to prepare mixed slurry, then putting the mixed slurry into a desilication reaction kettle, controlling the reaction temperature through steam heating, reacting the slurry at 100 ℃ for 2 hours, taking out the slurry after the reaction is finished, filtering, and measuring the modulus of the prepared water glass according to GB/T4209-2008 industrial sodium silicate. The results are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the method described in the present invention can prepare water glass product with high modulus by liquid phase method, the modulus of water glass can reach 3.5, Na in water glass2The content of O can meet the standard of industrial liquid water glass, the yield of the water glass reaches 69 percent, and the byproduct zeolite product realizes the complete utilization of the silica slag, reduces the energy consumption for preparing the high-modulus water glass and obtains a product with high added value.
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 (9)
1. A method for co-producing analcime from high-modulus water glass is characterized by comprising the following steps:
I) mixing the low-modulus water glass solution with the silica slag to perform hydrothermal reaction, and then performing solid-liquid separation to obtain a high-modulus water glass solution and filter residues;
II) washing and drying the filter residue to obtain analcime;
wherein SiO in the silicon slag2Is 50-80 wt%, Al2O3Is contained in an amount of 5 to 20% by weight.
2. The method as claimed in claim 1, wherein in step I), the hydrothermal reaction temperature is 120-200 ℃, the hydrothermal reaction time is 1-6h, and the hydrothermal reaction pressure is 0.2-2.0 MPa;
preferably, the hydrothermal reaction temperature is 150-.
3. The method as claimed in claim 1 or 2, characterized in that in step I), SiO is present in the silicon slag2In an amount of 70-80 wt.%, Al2O3The content of (A) is 8-15 wt%;
preferably, the silicon slag is selected from at least one of fly ash, coal gangue and silicon slag obtained after aluminum extraction from kaolinite;
preferably, the silicon slag contains SiO with amorphous phase2。
4. The method according to any one of claims 1 to 3, wherein in the step I), the mass ratio of the low-modulus water glass to the silica slag is 1: (2.5-5.0).
5. The method for preparing high-modulus water glass and coproducing analcite from silica slag is characterized by comprising the following steps of:
1) mixing the silicon slag with a sodium hydroxide solution to prepare mixed slurry;
2) carrying out desiliconization reaction on the slurry, and then carrying out solid-liquid separation to obtain a low-modulus water glass solution and first filter residue;
3) preparing the low-modulus water glass solution into a high-modulus water glass solution and analcime by the method for co-producing the high-modulus water glass and the analcime according to any one of claims 1 to 4;
wherein SiO in the silicon slag2Is 50-80 wt%, Al2O3Is contained in an amount of 5 to 20% by weight.
6. The method according to claim 5, wherein in the step 1), the mass ratio of the silicon slag to the sodium hydroxide solution is 1: (3-6), wherein the mass concentration of the sodium hydroxide solution is 10% -20%.
7. The method according to claim 5, wherein in the step 2), the desilication reaction temperature is 60-120 ℃, and the desilication reaction time is 0.5-2 h.
8. A method for preparing high-modulus water glass and coproducing analcite by using high-alumina fly ash is characterized by comprising the following steps:
a) contacting the high-alumina fly ash with an acid solution to carry out acid process aluminum extraction to prepare alumina and silica slag;
b) the silica slag is prepared into high-modulus water glass co-produced analcime by the method of any one of claims 5-8.
9. High modulus water glass and analcime prepared by a process according to any one of claims 1 to 8.
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