CN108584971B - Method for preparing high-modulus soluble silicate by utilizing gasified slag - Google Patents
Method for preparing high-modulus soluble silicate by utilizing gasified slag Download PDFInfo
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Abstract
The invention provides a method for preparing high-modulus soluble silicate by utilizing gasified slag, which comprises the following steps: (1) acid leaching is carried out on the gas-gasified slag, and after solid-liquid separation, activated gas-gasified slag and liquid phase are obtained; (2) carrying out desiliconization reaction on the activated fluidized slag and alkali liquor with the concentration of hydroxide ions of 1-5mol/L at 85-105 ℃, and then carrying out solid-liquid separation to obtain desiliconized liquid and solid phase; (3) and post-treating the desiliconized solution to obtain the high-modulus soluble silicate. Compared with the prior art, the method has the advantages of no need of adding any silicon source, wide raw material source, mild reaction condition, simple process, easy operation, higher quality of the obtained silicate product, modulus of 1.5-2.5, low production cost, no secondary solid and liquid pollutants, reduction of gasified slag, efficient resource utilization and remarkable economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical solid waste resource utilization, and relates to a method for preparing high-modulus soluble silicate by utilizing gasified slag.
Background
The coal gasification process is one of the main ways to produce synthesis gas products, and mainly comprises a fixed bed gasification technology, a fluidized bed gasification technology and a gas flow bed gasification technology, wherein solid coal is converted into gaseous synthesis gas, and byproducts such as steam, tar (individual gasification technology), ash and the like are simultaneously produced. With the great increase of the demand of synthesis gas products, the byproduct inorganic ash is also discharged and stockpiled in a large amount, which causes serious environmental pollution.
In order to solve the physical characteristics of ash generated in the coal gasification process, CN106336164A and CN106467376A respectively disclose a method for preparing a baking-free brick by utilizing gasified slag, the gasified slag is taken as a raw material, substances such as cement, bean sand stone or coal gangue, steel slag and the like are added into the raw material to adjust the composition proportion, the mixture is mixed, and a baking-free brick product is obtained after molding and curing; in order to improve the added value of ash utilization, CN104774023A and CN105130487A respectively disclose a method for preparing light ceramsite and filter ceramic by utilizing fly ash and gasified slag, the fly ash, the gasified slag and sodium/potassium feldspar are mixed according to a certain proportion, and then a small amount of auxiliary agent is added for the working procedures of molding, drying, firing and the like, so that qualified light ceramsite and filter ceramic products can be obtained. Based on the chemical composition characteristics, CN106800416A discloses a method for preparing a low-creep refractory brick from gasified slag, which comprises the steps of taking the gasified slag, cordierite, zirconia alumina, limestone, fly ash, feldspar and the like as raw materials, adding auxiliary agents such as boron carbide fiber, nano tungsten oxide and the like, and carrying out the working sections of fine grinding, microwave high-temperature sintering, washing, drying and the like to obtain a refractory material with high mechanical property, low creep property and good seismic resistance. Based on the characteristic of high carbon content of the gasified slag, CN102980195A discloses a method for treating the gasified slag in the coal chemical industry, which comprises the steps of uniformly mixing the gasified slag with coal slurry, adding white mud, and delivering the white mud to a fluidized bed boiler for combustion through a delivery pipeline, so as to improve the utilization efficiency of carbon in the white mud. However, the method still has the problems of low mixing proportion of the gasified slag, serious loss of valuable resources and the like, and cannot realize full-quantification and high-value utilization of the gasified slag.
The soluble silicate is a water-soluble silicate, the water solution of which is commonly called water glass, is an ore binder and has the characteristics of strong binding power, higher strength, good acid resistance/heat resistance and the like. Of the formula R2O·nSiO2In the formula, R2O is alkali metal oxide, n is the ratio of the mole number of silicon dioxide and alkali metal oxide, and is called the mole number of water glass, and is an important parameter for measuring the quality of silicate. The silicate with different modulus has different purposes, and can be widely applied to a plurality of fields such as common casting, precision casting, papermaking, ceramics, clay, mineral separation, kaolin, washing and the like.
At present, sodium silicate products with different modulus are mainly prepared by mixing silicon-containing raw ores (silica, quartz and the like) and alkali and sintering at high temperature. CN106829983A, CN107215878A and CN107720766A disclose respectively that a silicon-containing mineral (fluorine-containing silicon slag, rice hull ash or coal gangue) is mixed with sodium carbonate, and sintering reaction is performed at high temperature to obtain sodium silicate products with different qualities. CN106966403A discloses a method for producing liquid sodium silicate, which is to react quartz with sodium hydroxide solution for a long time under a high-temperature and high-pressure system to prepare a high-quality sodium silicate product with a modulus of 3.2-3.4. But the silicon source reaction activity is low in the process of producing sodium silicate products, the reaction strip requirement is harsh, the energy consumption and material consumption in the reaction process are high, and the economic and environmental benefits are not obvious.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing high-modulus soluble silicate by utilizing gasified slag, which can realize the large dissolution of silicon under mild reaction conditions by the mutual matching of acid activation and controllable desiliconization, improve the modulus of the soluble silicate in a liquid phase, can obtain a high-quality soluble silicate product with the modulus of 1.5-2.5 without adding any silicon source, does not generate secondary solid and liquid pollutants, realizes the reduction and the efficient recycling of the gasified slag, and has remarkable economic and environmental benefits.
In the present invention, unless otherwise specified, the liquid-solid ratio refers to the mass ratio of liquid to solid.
The high modulus soluble silicate means that the modulus of the soluble silicate is 1.5-2.5.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing high-modulus soluble silicate by utilizing gasified slag, which comprises the following steps:
(1) leaching the gasified slag by acid liquor, and performing solid-liquid separation to obtain activated gasified slag and a liquid phase;
(2) carrying out desiliconization reaction on the activated fluidized slag and alkali liquor with the concentration of hydroxide ions of 1-5mol/L at 85-105 ℃, and then carrying out solid-liquid separation to obtain desiliconized liquid and solid phase;
(3) and post-treating the desiliconized solution to obtain the high-modulus soluble silicate.
According to the invention, the gasification slag is leached and activated, and is matched with subsequent controllable desilication, so that a high-quality soluble silicate product with the modulus of 1.5-2.5 can be prepared, secondary solid and liquid pollutants are not generated, the reduction of the gasification slag and the efficient utilization of resources are realized, and the economic and environmental benefits are obvious. Compared with the prior art, the method for preparing the soluble silicate does not need to add any silicon source, has wide raw material source, mild reaction condition, simple process and easy operation.
The preparation method provided by the invention can be used for controllable desiliconization by controlling the concentration of the alkali liquor and the reaction temperature of the alkali liquor and the activated gasification slag, so that more than 60% (mass percentage content) of silicon in the activated gasification slag is removed. The concentration of the alkali liquor in the controllable desiliconization process is 1-5mol/L, such as 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.8mol/L, 4.3mol/L or 4.8 mol/L; the reaction temperature of the alkali liquor and the activated gasification slag is 85-105 ℃, such as 88 ℃, 90 ℃, 95 ℃, 100 ℃ or 103 ℃. If the ratio is outside the above range, the desiliconization efficiency is low and the modulus of the soluble silicate in the liquid phase is low.
The silicon in the gasified slag has low reactivity and cannot be decomposed and removed into a solution under the low-temperature dilute alkali condition, and the activity of the silicon in the gasified slag can be obviously improved by activating the gasified slag with acid, so that the modulus of soluble silicate in the desiliconized solution is obviously improved.
The solid-liquid separation in step (1) and step (2) is a conventional operation in the art, and typical but non-limiting solid-liquid separation means such as centrifugation or filtration.
The acid in the step (1) not only has the activation effect, but also can reduce the content of impurities in the gasified slag and simultaneously improve the reaction activity of the glass phase silicon dioxide.
The acid in step (1) is selected from any one or a combination of at least two of hydrochloric acid, sulfuric acid or nitric acid, and typical but non-limiting combinations are hydrochloric acid and sulfuric acid, hydrochloric acid and nitric acid, sulfuric acid and nitric acid and the like.
Preferably, the hydrochloric acid is selected from industrial by-product hydrochloric acid and/or industrial hydrochloric acid.
Preferably, the hydrogen ion concentration of the acid in step (1) is 3 to 10mol/L, such as 3.5mol/L, 4.5mol/L, 4.8mol/L, 5.2mol/L, 5.8mol/L, 6.0mol/L, 7.0mol/L, 8.0mol/L, 9.5mol/L or 9.8mol/L, etc.
Preferably, the liquid-solid ratio of the acid to the gasified residue in the step (1) is 3:1-8:1, such as 4:1, 5:1, 6:1 or 7: 1.
The leaching temperature in the step (1) is 75-95 ℃, such as 78 ℃, 80 ℃, 85 ℃, 88 ℃ or 92 ℃ and the like.
Preferably, the leaching time in step (1) is 60-180min, such as 80min, 100min, 120min or 150 min.
Preferably, the leaching in step (1) is carried out under water bath conditions.
The step (1) is as follows: and (3) circularly leaching the gasified slag by using hydrochloric acid, and performing solid-liquid separation to obtain activated gasified slag and a liquid phase. And (3) circularly leaching the gasified slag by using hydrochloric acid to obtain an aluminum-rich liquid phase, and further preparing the polyaluminium chloride. The cyclic leaching means that hydrochloric acid is used for activating gasified slag during the first leaching, and leaching is carried out after the previous leaching liquid is used for leaching the previous leaching slag until the cycle is finished.
Preferably, the number of the circulation is more than 5, such as 5, 6, 7, 8, 9, 10 or 15, and the like, and the aluminum ion concentration in the liquid phase can be increased to 50-60g/L after more than 5 circulations, and the content (mass percentage content) of the aluminum oxide can reach more than 7.5-9.5%.
Preferably, part of the hydrochloric acid is supplemented in the circulation process of the circulation leaching, and the part means that the additional hydrochloric acid accounts for more than 0 and less than 100 percent of the volume of the total leaching agent.
Preferably, the concentration of the supplemented hydrochloric acid is more than 300g/L, such as 310g/L, 320g/L, 350g/L, 380g/L, 390g/L, 420g/L or 450g/L, and the like, and the best leaching effect can be achieved.
And carrying out polymerization reaction on the liquid phase and alkaline salt, and curing to obtain the polyaluminium chloride.
Preferably, the basic salt is selected from any one of calcium aluminate, calcium oxide or calcium-based solid waste or a combination of at least two of them. Typical but non-limiting combinations are calcium aluminate and calcium oxide, calcium aluminate and calcium based solid waste, calcium aluminate, calcium oxide and calcium based solid waste.
Preferably, the calcium-based solid waste is selected from industrial waste phosphorous slag and/or high calcium fluidized bed fly ash.
Preferably, the liquid-to-solid ratio of the liquid phase to the basic salt is 6-15mL/g, such as 7mL/g, 8mL/g, 9mL/g, 10mL/g, 11mL/g, 12mL/g, or 14mL/g, and the like.
Preferably, the basic salt is added to the liquid phase 2-4 times, e.g. 3 times etc.
Preferably, part of the alkaline salt is added into the liquid phase every 0.5-1.5h, if the adding time of the batch is too long, the hydrochloric acid in the system is volatilized to reduce the acidity, so that the dissolution of the alkaline salt is reduced, the alkaline salt is wasted, and the salinity of the product is reduced; if the time of adding the alkaline salt in batches is too short, the alkaline salt cannot be dissolved sufficiently and quickly, and the alkaline salt is wasted.
Preferably, the polymerization temperature is 75-95 deg.C, such as 78 deg.C, 80 deg.C, 85 deg.C, 88 deg.C or 92 deg.C.
Preferably, the polymerization reaction time is 60-210min, such as 80min, 100min, 120min, 150min, 180min or 200 min.
Preferably, the polymerization is carried out while controlling the pH to 3 to 5, such as 4, etc.
Preferably, the temperature of the curing is 45-75 ℃, such as 50 ℃, 60 ℃, 65 ℃ or 72 ℃ and the like.
Preferably, the curing time is 18-36h, such as 20h, 22h, 25h, 28h, 30h or 34 h.
As a preferable technical scheme, the step (1) is as follows: circularly leaching the gasified slag by hydrochloric acid with hydrogen ion concentration of 4-10mol/L according to a liquid-solid ratio of 3:1-8:1, circulating for more than 5 times, wherein the temperature of the circular leaching is 75-95 ℃, the time of each leaching is 60-180min, part of hydrochloric acid with concentration of more than 300g/L is supplemented in the circulating process, and the circular leaching is carried out under the water bath condition to obtain activated gasified slag and a liquid phase;
preferably, the liquid phase and the alkaline salt are subjected to polymerization reaction for 60-210min at the temperature of 75-95 ℃, the liquid-solid ratio of the liquid phase to the alkaline salt is 6-15mL/g, wherein partial alkaline salt is added into the liquid phase every 0.5-1.5h, the alkaline salt is added into the liquid phase for 2-4 times, and then aging is carried out for 18-36h at the temperature of 45-75 ℃ to obtain the polyaluminium chloride.
The hydrochloric acid is utilized for cyclic leaching, so that the polyaluminium chloride preparation method has the following advantages: the content of the alumina in the liquid phase can be increased only by circulating leaching, the concentration of the aluminum ions in the liquid phase can be increased to 50-60g/L, and simultaneously, the content (mass percentage content) of the alumina reachesMore than 7.5 percent, no need of adding any aluminum source, simple operation process, large operation flexibility, low impurity content of activated gasification slag after acid leaching, and Fe2O3The content is reduced from 9 percent to about 1 percent, the content of CaO is reduced from 6 percent to about 1 percent, and Na is added2The O content is reduced from 3 percent to about 0.5 percent, and no secondary pollutant is generated in the process, thereby providing a high-quality raw material for the preparation and the utilization of the silicon-based material as a building material and realizing the joint development of economic and environmental benefits; the method for preparing the polyaluminium chloride by utilizing the gasified slag has mild reaction conditions, provides a new technology and a new raw material for the preparation industry of the polyaluminium chloride, and relieves the exhaustion of high-quality bauxite resources in China; the gasified slag is replaced by other materials, and the polyaluminium chloride can not be prepared by adopting a circulating leaching method.
The polyaluminium chloride product obtained by the method has the alumina content (mass percentage) of more than 7.8 percent, the basicity of 54 to 82 percent and the density of 1.15g/cm3The above.
The alkali liquor in the step (2) is selected from sodium hydroxide solution and/or potassium hydroxide solution. The alkali solution may be other substances as long as the metal ions thereof can form soluble salts with silicate ions.
The liquid-solid ratio of the alkali liquor to the activated gasification slag is 3:1-6:1, such as 3.5:1, 4.0:1, 4.5:1, 4.8:1, 5.2:1, 5.5:1 or 5.8: 1.
Preferably, the desiliconization reaction time in step (2) is 90-240min, such as 110min, 130min, 150min, 180min, 190min, 210min or 230 min.
And (3) drying the solid phase in the step (2) and then preparing the adsorbing material.
The post-treatment of the step (3) comprises: the desilication solution is concentrated to 60% -90% of the original volume, such as 65%, 70%, 75%, 80%, 85% or 88%.
Preferably, the concentration is evaporative concentration.
Preferably, the steam generated during the evaporative concentration is used to prepare the acid and/or base solution required in step (1) and/or step (2) after cooling.
Preferably, the temperature after cooling is 55-85 ℃, such as 58 ℃, 60 ℃, 65 ℃, 70 ℃, 78 ℃ or 82 ℃ and the like.
As the most preferred technical scheme, the method comprises the following steps:
(1) circularly leaching the gasified slag by hydrochloric acid with hydrogen ion concentration of 3-10mol/L according to a liquid-solid ratio of 3:1-8:1, circulating for more than 5 times, wherein the temperature of the circular leaching is 75-95 ℃, the time of each leaching is 60-180min, part of hydrochloric acid with concentration of more than 300g/L is supplemented in the circulating process, and the circular leaching is carried out under the water bath condition to obtain activated gasified slag and a liquid phase;
(2) carrying out polymerization reaction on the liquid phase and alkaline salt for 60-210min under the conditions that the temperature is 75-95 ℃ and the pH is 3-5, wherein the liquid-solid ratio of the liquid phase to the alkaline salt is 6-15mL/g, adding partial alkaline salt into the liquid phase every 0.5-1.5h, adding the alkaline salt into the liquid phase for 2-4 times, and then curing for 18-36h under the condition of 45-75 ℃ to obtain polyaluminium chloride;
(3) carrying out desiliconization reaction on alkali liquor with the concentration of hydroxyl ions of 1-5mol/L and activated gasification slag at 85-105 ℃ according to the liquid-solid ratio of 3:1-6:1, wherein the desiliconization reaction time is 90-240min, and then carrying out solid-liquid separation to obtain desiliconized liquid and solid phase;
(4) evaporating and concentrating the desiliconized solution to 60% -90% of the original volume to obtain high-modulus soluble silicate;
wherein, the step (2) and the step (3) have no sequence.
The modulus of the soluble silicate obtained by the method for preparing the high-modulus soluble silicate by using the gasified slag is 1.5-2.5, the quality is high, and the method can be widely applied to the fields of coatings, concrete, silica gel, waterproof agents and the like.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for preparing the high-modulus soluble silicate by utilizing the gasification slag, disclosed by the invention, through the mutual matching of acid activation and controllable desiliconization, the silicon can be greatly dissolved out under a mild reaction condition, more than 60% (mass percentage content) of silicon can be removed, the modulus of the soluble silicate in a liquid phase is improved, a high-quality silicate product with the modulus of 1.5-2.5 can be obtained, secondary solid and liquid pollutants are not generated, the reduction and the resource utilization of the gasification slag are realized, and the economic and environmental benefits are obvious.
Compared with the prior art, the method for preparing the high-modulus soluble silicate by utilizing the gasified slag does not need to add any silicon source, has wide raw material sources, mild reaction conditions, high operation flexibility, simple process and easy operation, and provides a new technology and a new raw material for industries taking the high-modulus soluble silicate as the raw material.
The method for preparing the high-modulus soluble silicate by using the gasified slag can co-produce polyaluminium chloride, can improve the content of the alumina in the liquid phase only by circular leaching, can improve the concentration of aluminum ions in the liquid phase to 50-60g/L, simultaneously has the content (mass percentage content) of the alumina of more than 7.5 percent, has mild reaction conditions, does not need to add any aluminum source, has simple operation process and large operation elasticity, has low impurity content of activated gasified slag after acid leaching, and has Fe2O3The content is reduced from 9 percent to about 1 percent, the content of CaO is reduced from 6 percent to about 1 percent, and Na is added2The content of O is reduced from 3 percent to about 0.5 percent, a high-quality raw material is provided for the preparation and building material utilization of silicon-based materials, a new technology and a new raw material are provided for the preparation industry of polyaluminium chloride, and the exhaustion of high-quality bauxite resources in China is relieved.
Drawings
Fig. 1 is a process flow chart for preparing high-modulus sodium silicate by using gasified slag according to an embodiment of the invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
A process for preparing high-modulus sodium silicate by using gasification slag, as shown in fig. 1, the process comprises the following steps:
(1) leaching the gasified slag by acid liquor, and performing solid-liquid separation to obtain activated gasified slag and a liquid phase;
(2) carrying out desiliconization reaction on the activated gasification slag and a sodium hydroxide solution with the hydroxide ion concentration of 1-5mol/L at 85-105 ℃, and then carrying out solid-liquid separation to obtain desiliconized liquid and a solid phase;
(3) and (4) evaporating the desiliconized solution to obtain the high-modulus sodium silicate.
Example 1
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and industrial byproduct hydrochloric acid according to a liquid-solid ratio of 8:1, wherein the concentration of the hydrochloric acid is 3mol/L, the reaction temperature is 95 ℃, the reaction time is 90min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 2mol/L, the reaction temperature is 90 ℃, the reaction time is 120min, the liquid-solid ratio is 5:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 80% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the temperature of the evaporated water is reduced to 65 ℃;
the modulus of the obtained sodium silicate product is 1.95.
Example 2
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and nitric acid according to a liquid-solid ratio of 7:1, wherein the concentration of the nitric acid is 4mol/L, the reaction temperature is 90 ℃, the reaction time is 120min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 3mol/L, the reaction temperature is 95 ℃, the reaction time is 150min, the liquid-solid ratio is 3:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 90% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the evaporating water temperature is reduced to 55 ℃;
the modulus of the obtained sodium silicate product is 2.17.
Example 3
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and industrial byproduct hydrochloric acid according to a liquid-solid ratio of 4:1, wherein the concentration of the hydrochloric acid is 9mol/L, the reaction temperature is 80 ℃, the reaction time is 180min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 2mol/L, the reaction temperature is 105 ℃, the reaction time is 120min, the liquid-solid ratio is 5:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 70% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the temperature of the evaporated water is reduced to 75 ℃;
the modulus of the obtained sodium silicate product is 2.42.
Example 4
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and industrial byproduct hydrochloric acid according to a liquid-solid ratio of 6:1, wherein the concentration of the hydrochloric acid is 6mol/L, the reaction temperature is 95 ℃, the reaction time is 60min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 4mol/L, the reaction temperature is 85 ℃, the reaction time is 180min, the liquid-solid ratio is 4:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 85% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the temperature of the evaporated water is reduced to 65 ℃;
the modulus of the obtained sodium silicate product is 1.94.
Example 5
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and sulfuric acid according to a liquid-solid ratio of 3:1, wherein the concentration of the sulfuric acid is 5mol/L, the reaction temperature is 75 ℃, the reaction time is 180min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 3mol/L, the reaction temperature is 85 ℃, the reaction time is 90min, the liquid-solid ratio is 3:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 90% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the evaporating water temperature is reduced to 55 ℃;
the modulus of the obtained sodium silicate product is 1.58.
Example 6
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and industrial byproduct hydrochloric acid according to a liquid-solid ratio of 5:1, wherein the concentration of the hydrochloric acid is 5mol/L, the reaction temperature is 85 ℃, the reaction time is 120min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 3mol/L, the reaction temperature is 105 ℃, the reaction time is 180min, the liquid-solid ratio is 4:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 85% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the temperature of the evaporated water is reduced to 65 ℃;
the modulus of the obtained sodium silicate product is 2.06.
Example 7
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and sulfuric acid according to a liquid-solid ratio of 4:1, wherein the concentration of the sulfuric acid is 4mol/L, the reaction temperature is 95 ℃, the reaction time is 180min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 2mol/L, the reaction temperature is 95 ℃, the reaction time is 120min, the liquid-solid ratio is 3:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 70% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the temperature of the evaporated water is reduced to 65 ℃;
the modulus of the obtained sodium silicate product is 1.83.
Example 8
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and nitric acid according to a liquid-solid ratio of 7:1, wherein the concentration of sulfuric acid is 6mol/L, the reaction temperature is 90 ℃, the reaction time is 150min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 4mol/L, the reaction temperature is 90 ℃, the reaction time is 180min, the liquid-solid ratio is 4:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 75% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the evaporating water temperature is reduced to 55 ℃;
the modulus of the obtained sodium silicate product is 2.31.
Example 9
A process for preparing potassium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and industrial byproduct hydrochloric acid according to a liquid-solid ratio of 8:1, wherein the concentration of the hydrochloric acid is 3mol/L, the reaction temperature is 95 ℃, the reaction time is 90min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute potassium hydroxide solution, wherein the alkali concentration is 1mol/L, the reaction temperature is 100 ℃, the reaction time is 240min, the liquid-solid ratio is 6:1, and the rotating speed is 350 r/min; after the reaction is finished, performing solid-liquid separation to obtain a potassium silicate crude product;
and (3) evaporation and concentration: evaporating and concentrating the crude potassium silicate product to 60% of the original volume, and conveying the crude potassium silicate product to an acid leaching and dilute alkali desiliconization section when the temperature of the evaporated water is reduced to 85 ℃;
the modulus of the obtained potassium silicate product is 1.78.
Example 10
A process for preparing sodium silicate by utilizing gasification slag comprises the following steps:
and (3) dissolution process: the method comprises the following steps of carrying out mixed reaction on gasified slag and sulfuric acid according to a liquid-solid ratio of 8:1, wherein the concentration of hydrochloric acid is 10mol/L, the reaction temperature is 95 ℃, the reaction time is 90min, and the rotating speed is 350 r/min; after the reaction is finished, activated gasified slag is obtained through solid-liquid separation;
a desiliconization process: reacting the activated gasified slag with a dilute sodium hydroxide solution, wherein the alkali concentration is 5mol/L, the reaction temperature is 90 ℃, the reaction time is 180min, the liquid-solid ratio is 4:1, and the rotating speed is 350 r/min; after the reaction is finished, obtaining a sodium silicate crude product through solid-liquid separation;
and (3) evaporation and concentration: evaporating and concentrating the sodium silicate crude product to 70% of the original volume, and conveying the sodium silicate crude product to an acid leaching and dilute alkali desiliconization section when the evaporating water temperature is reduced to 60 ℃;
the modulus of the obtained sodium silicate product is 2.15.
Example 11
A process for preparing sodium silicate using gasification slag, which is the same as example 1 except that the digestion process is as follows:
the method comprises the following steps of carrying out mixed reaction on gasified slag and industrial byproduct hydrochloric acid according to a liquid-solid ratio of 6:1, wherein the concentration of the hydrochloric acid is 200g/L, the reaction temperature is 95 ℃, the reaction time is 180min, and the rotating speed is 350 r/min; after the reaction is finished, obtaining filtrate through solid-liquid separation;
adding fresh industrial byproduct hydrochloric acid (the mass percentage content is 30%) into the filtrate to prepare the required volume (the liquid-solid ratio is 6:1 during leaching), carrying out the acid leaching process, repeating the process, circulating for 9 times, and filtering to obtain an aluminum-rich solution and activated gasified slag, wherein the content (mass percentage content) of aluminum oxide in the aluminum-rich acid solution is up to 8.2%;
adding industrial waste phosphorus slag (CaO content is more than 30 mass percent) into the aluminum-rich solution for 4 times, wherein the adding interval time is 0.5h, performing polymerization regulation, controlling the pH to be 3-5, the liquid-solid ratio to be 6mL/g, the polymerization temperature to be 95 ℃, the polymerization time to be 210min, the curing temperature to be 65 ℃, and the curing time to be 36 h.
The obtained polyaluminium chloride product has the alumina content (mass percentage content) of 8.4 percent, the basicity of 56 percent and the density of 1.15g/cm3。
The modulus of the obtained sodium silicate product is 2.08.
Example 12
A process for preparing sodium silicate using gasification slag, which is the same as example 1 except that the digestion process is as follows:
the method comprises the following steps of carrying out mixed reaction on gasified slag and industrial byproduct hydrochloric acid according to a liquid-solid ratio of 8:1, wherein the concentration of the hydrochloric acid is 220g/L, the reaction temperature is 85 ℃, the reaction time is 120min, and the rotation speed is 350 r/min; after the reaction is finished, obtaining filtrate through solid-liquid separation;
adding fresh industrial byproduct hydrochloric acid (the mass percentage content is 30%) into the filtrate to prepare the required volume (the liquid-solid ratio is 8:1 during leaching), carrying out the acid leaching process, repeating the process, circulating for 7 times, and filtering to obtain an aluminum-rich solution and activated gasified slag, wherein the content (mass percentage content) of aluminum oxide in the aluminum-rich acid solution is up to 7.8%;
adding industrial waste phosphorus slag (CaO content is more than 30 mass percent) into the aluminum-rich solution for 2 times, wherein the adding interval time is 1.5h, performing polymerization regulation, controlling the pH to be 3-5, the liquid-solid ratio to be 10mL/g, the polymerization temperature to be 85 ℃, the polymerization time to be 180min, the curing temperature to be 75 ℃, and the curing time to be 30 h.
The obtained polyaluminium chloride product has the alumina content (mass percentage content) of 8.2 percent, the basicity of 61 percent and the density of 1.17g/cm3。
The modulus of the obtained sodium silicate product is 1.84.
Example 13
A process for preparing sodium silicate using gasification slag, which is the same as example 1 except that the digestion process is as follows:
the method comprises the following steps of carrying out mixed reaction on gasified slag and industrial byproduct hydrochloric acid according to a liquid-solid ratio of 3:1, wherein the concentration of the hydrochloric acid is 220g/L, the reaction temperature is 75 ℃, the reaction time is 60min, and the rotating speed is 350 r/min; after the reaction is finished, obtaining filtrate through solid-liquid separation;
adding fresh industrial byproduct hydrochloric acid (the mass percentage content is 30%) into the filtrate to prepare the required volume (the liquid-solid ratio is 3:1 during leaching), carrying out the acid leaching process, repeating the process, circulating for 7 times, and filtering to obtain an aluminum-rich solution and activated gasified slag, wherein the content (mass percentage content) of aluminum oxide in the aluminum-rich acid solution is up to 7.6%;
adding calcium oxide into the aluminum-rich solution for 3 times, wherein the adding interval time is 1h, performing polymerization regulation, controlling the pH to be 3-5, the liquid-solid ratio to be 15mL/g, the polymerization temperature to be 75 ℃, the polymerization time to be 60min, the curing temperature to be 45 ℃, and the curing time to be 18 h.
The obtained polyaluminium chloride product has the alumina content (mass percentage) of 8.0 percent, the basicity of 62 percent and the density of 1.15g/cm3。
The mole number of the obtained sodium silicate product is 1.95.
Comparative example 1
The same as example 1 except that the gasified slag in example 1 was replaced with any one or a combination of at least two of bauxite, kaolin, and high-alumina fly ash.
The modulus of the obtained sodium silicate product is 0.46-0.63.
Comparative example 2
The same procedure as in example 1 was repeated, except that the acid leaching was not conducted on the degassed and digested residue, and the residue was directly subjected to desiliconization with a dilute sodium hydroxide solution.
The modulus of the obtained sodium silicate product is 0.32.
Comparative example 3
The procedure of example 1 was repeated, except that the alkali concentration in the desiliconization was 5.5 mol/L.
The modulus of the obtained sodium silicate product is 1.25.
Comparative example 4
The procedure of example 1 was repeated, except that the alkali concentration in the desiliconization was 0.5 mol/L.
The modulus of the obtained sodium silicate product is 1.42.
Comparative example 5
The procedure of example 1 was repeated, except that the reaction temperature during the desilication was 80 ℃.
The modulus of the obtained sodium silicate product is 1.04.
Comparative example 6
The procedure of example 1 was repeated, except that the reaction temperature during the desilication was 110 ℃.
The modulus of the obtained sodium silicate product is 1.47.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (31)
1. The method for preparing the high-modulus soluble silicate by using the gasified slag is characterized by comprising the following steps of:
(1) acid leaching the gasified slag by using hydrogen ions with the concentration of 3-10mol/L, and performing solid-liquid separation to obtain activated gasified slag and a liquid phase;
(2) carrying out desiliconization reaction on the activated fluidized slag and alkali liquor with the concentration of hydroxide ions of 1-5mol/L at 85-105 ℃, and then carrying out solid-liquid separation to obtain desiliconized liquid and solid phase;
(3) post-treating the desiliconized solution to obtain soluble silicate with the modulus of 1.5-2.5;
the post-treatment of the step (3) comprises: and concentrating the desiliconized solution to 60% -90% of the original volume.
2. The method according to claim 1, wherein the acid in step (1) is selected from any one of hydrochloric acid, sulfuric acid or nitric acid or a combination of at least two of the acids.
3. The method according to claim 2, wherein the hydrochloric acid is selected from industrial by-product hydrochloric acid and/or industrial hydrochloric acid.
4. The method according to claim 1, wherein the liquid-solid ratio of the acid to the gasified slag in the step (1) is 3:1 to 8: 1.
5. The method as claimed in claim 1, wherein the temperature of the leaching in step (1) is 75-95 ℃.
6. The method as claimed in claim 1, wherein the leaching time in step (1) is 60-180 min.
7. The method of claim 1, wherein the leaching of step (1) is performed under water bath conditions.
8. The method of claim 1, wherein step (1) is: and (3) circularly leaching the gasified slag by using hydrochloric acid, and performing solid-liquid separation to obtain activated gasified slag and a liquid phase.
9. The method of claim 8, wherein the number of cycles is 5 or more.
10. The method of claim 8, wherein additional hydrochloric acid is added during the cycle of the cyclic leaching.
11. The method of claim 10, wherein the supplemental hydrochloric acid has a concentration greater than 300 g/L.
12. The method as claimed in claim 1, wherein the liquid phase is polymerized with an alkaline salt and aged to obtain polyaluminum chloride.
13. The method of claim 12, wherein the basic salt is selected from any one of calcium aluminate, calcium oxide, or calcium-based solid waste, or a combination of at least two thereof.
14. The method of claim 13, wherein the calcium-based solid waste is selected from industrial waste phosphorous slag and/or high calcium fluidized bed fly ash.
15. The method of claim 12, wherein the liquid-to-solid ratio of the liquid phase to the basic salt is 6-15 mL/g.
16. The method according to claim 12, wherein the basic salt is added to the liquid phase 2-4 times.
17. The method of claim 16, wherein the partial alkaline salt is added to the liquid phase every 0.5 to 1.5 hours.
18. The process according to claim 12, wherein the temperature of the polymerization reaction is 75-95 ℃.
19. The process according to claim 12, wherein the polymerization time is 60-210 min.
20. The method according to claim 12, wherein the pH is controlled to 3 to 5 during the polymerization.
21. The method of claim 12, wherein the temperature of said aging is 45-75 ℃.
22. The method of claim 12, wherein the aging time is 18-36 hours.
23. The method of claim 1, wherein step (1) is: circularly leaching the gasified slag by hydrochloric acid with the hydrogen ion concentration of 4-10mol/L according to the liquid-solid ratio of 3:1-8:1, circulating for more than 5 times, wherein the temperature of the circular leaching is 75-95 ℃, the time of each leaching is 60-180min, part of hydrochloric acid with the concentration of more than 300g/L is supplemented in the circulating process, and the circular leaching is carried out under the water bath condition to obtain the activated gasified slag and a liquid phase.
24. The method as claimed in claim 23, wherein the liquid phase and the alkaline salt are polymerized at a temperature of 75-95 ℃ for 60-210min, and the liquid-solid ratio of the liquid phase to the alkaline salt is 6-15mL/g, wherein part of the alkaline salt is added to the liquid phase every 0.5-1.5h, the alkaline salt is added to the liquid phase 2-4 times, and then the liquid phase is aged at 45-75 ℃ for 18-36h to obtain the polyaluminium chloride.
25. The method according to claim 1, wherein the lye of step (2) is selected from the group consisting of sodium hydroxide solution and/or potassium hydroxide solution.
26. The method as claimed in claim 1, wherein the liquid-solid ratio of the alkali liquor to the activated gasified slag is 3:1-6: 1.
27. The method according to claim 1, wherein the desilication reaction time in the step (2) is 90-240 min.
28. The method of claim 1, wherein the concentrating is evaporative concentrating.
29. The method according to claim 28, wherein the steam generated during the evaporative concentration is used to prepare the acid and/or base solution required in step (1) and/or step (2) after cooling.
30. The method of claim 29, wherein the cooled temperature is 55-85 ℃.
31. Method according to claim 1, characterized in that it comprises the following steps:
(1) circularly leaching the gasified slag by hydrochloric acid with hydrogen ion concentration of 3-10mol/L according to a liquid-solid ratio of 3:1-8:1, circulating for more than 5 times, wherein the temperature of the circular leaching is 75-95 ℃, the time of each leaching is 60-180min, part of hydrochloric acid with concentration of more than 300g/L is supplemented in the circulating process, and the circular leaching is carried out under the water bath condition to obtain activated gasified slag and a liquid phase;
(2) carrying out polymerization reaction on the liquid phase and alkaline salt for 60-210min under the conditions that the temperature is 75-95 ℃ and the pH is 3-5, wherein the liquid-solid ratio of the liquid phase to the alkaline salt is 6-15mL/g, adding partial alkaline salt into the liquid phase every 0.5-1.5h, adding the alkaline salt into the liquid phase for 2-4 times, and then curing for 18-36h under the condition of 45-75 ℃ to obtain polyaluminium chloride;
(3) carrying out desiliconization reaction on alkali liquor with the concentration of hydroxyl ions of 1-5mol/L and activated gasification slag at 85-105 ℃ according to the liquid-solid ratio of 3:1-6:1, wherein the desiliconization reaction time is 90-240min, and then carrying out solid-liquid separation to obtain desiliconized liquid and solid phase;
(4) evaporating and concentrating the desiliconized solution to 60% -90% of the original volume to obtain high-modulus soluble silicate;
wherein, the step (2) and the step (3) have no sequence.
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| CN110616320B (en) * | 2019-09-17 | 2020-07-31 | 北京科技大学 | Method for desiliconizing silicon-containing ore or slag |
| CN111060417B (en) * | 2019-11-25 | 2023-03-21 | 中国石油化工股份有限公司 | Quantitative analysis method for gasified slag mineral phase |
| CN113045341A (en) * | 2019-12-26 | 2021-06-29 | 国家能源投资集团有限责任公司 | Method for preparing alkali-free silicon fertilizer from silicon-containing acid treatment solution and alkali-free silicon fertilizer |
| CN112661162B (en) * | 2020-12-16 | 2023-04-28 | 青岛惠城环保科技集团股份有限公司 | Treatment method of petroleum coke hydrogen production ash slag and mesoporous silicon material |
| CN116078348A (en) * | 2021-11-08 | 2023-05-09 | 中国科学院过程工程研究所 | Comprehensive utilization method of gas slag |
| CN116102187A (en) * | 2021-11-09 | 2023-05-12 | 中国科学院过程工程研究所 | Method for detoxifying gasified slag activated acid liquor and comprehensively utilizing gasified slag activated acid liquor as resources |
| CN114985435B (en) * | 2022-08-05 | 2023-01-10 | 中国科学院过程工程研究所 | Method for comprehensively utilizing waste salt and various solid wastes |
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| CN117339552B (en) * | 2023-11-21 | 2024-06-21 | 陕西科技大学 | Gas-based residue adsorption-flocculation multifunctional water purifying agent and preparation method and application thereof |
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