CN110713199A - Treatment method of gallium extraction waste liquid obtained after extracting aluminum and gallium by fly ash acid method and water purifying agent - Google Patents
Treatment method of gallium extraction waste liquid obtained after extracting aluminum and gallium by fly ash acid method and water purifying agent Download PDFInfo
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- CN110713199A CN110713199A CN201911085837.XA CN201911085837A CN110713199A CN 110713199 A CN110713199 A CN 110713199A CN 201911085837 A CN201911085837 A CN 201911085837A CN 110713199 A CN110713199 A CN 110713199A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
Abstract
A treatment method of gallium extraction waste liquid obtained after extracting aluminum and gallium by a fly ash acid method comprises the following steps: (1) separating and purifying the gallium extraction waste liquid to obtain ferric chloride solution and residual waste liquid; (2) adding a polymerization agent into the ferric chloride solution to carry out polymerization reaction; then standing and curing or drying the solution after the polymerization reaction to obtain a poly ferric chloride water purifying agent; (3) adding fly ash into the residual waste liquid, uniformly mixing, then placing the mixture into a reaction kettle for reaction, cooling the slurry after the reaction, and performing solid-liquid separation to obtain a solid material and a liquid material; (4) adding calcium aluminate into the liquid material to carry out polymerization reaction to obtain a polyaluminium chloride solution; (5) and drying the polyaluminium chloride solution to obtain the solid polyaluminium chloride water purifying agent. The treatment method can realize resource recycling of iron, aluminum and hydrochloric acid in the gallium extraction waste liquid, avoid resource waste and simultaneously obtain the poly-ferric chloride water purifying agent and the poly-aluminum chloride water purifying agent.
Description
Technical Field
The invention belongs to the field of coal, and particularly relates to a treatment method of gallium extraction waste liquid obtained after extracting aluminum and gallium by a fly ash acid method and a water purifying agent.
Background
The Ore district of Ore and Tougeli in the middle and west of inner Mongolia has a large amount of high-quality coal resources, the coal in this area has low volatile content (less than or equal to 10%), low sulfur, the characteristic of extra low phosphorus, and contain abundant metallic aluminium, gallium and rare earth resource in the coal, it is the ideal clean energy. After the coal is generated by a coal-fired power plant, the aluminum, the gallium and the rare earth elements which are rich in the coal are all enriched in the coal ash.
The coal ash of coal-fired power plants currently has the largest solid garbage emission amount in China, and if a large amount of coal ash is not treated, dust can be generated to pollute the atmosphere; if the water system is drained, river congestion can be caused, and toxic chemicals in the water system can cause harm to human bodies and organisms.
The technology for extracting aluminum oxide by the fly ash acid method initiated by the national energy group is operated by seven pilot-scale tests at present, and the metallurgical grade first-grade product aluminum oxide and the 4N grade gallium product are produced, so that the process technology is feasible, the equipment is reliable, the safety and the environmental protection reach the standard, and the industrial conditions are met. The technology solves the difficult problem of solid waste stockpiling of coal-fired power plants, and simultaneously realizes the efficient utilization of resources (aluminum and gallium) in coal.
Extracting alumina from fly ash by hydrochloric acid method, and extracting gallium to obtain gallium-extracted waste liquid containing high-concentration iron ions, aluminum ions, hydrogen ions and small amount of impurity ions (K)+、Na+、Ca2+、SiO2) The acid waste liquid is brownish red; meanwhile, the content of iron, aluminum and hydrochloric acid in the gallium extraction waste liquid is high (Fe)3+The content of Al is 60-110g/L3+The content is 20-60g/L, H+The content is 0.5-5mol/L), the sum of the contents of the rest ions (which can be regarded as impurity ions) is not more than 3.5g/L, and the preparation of the polyferric chloride water purifying agent and/or the polyaluminum chloride water purifying agent is basically not influenced, so the method has great resource utilization value. If the environment-friendly treatment or resource recycling is not adopted, the environment is seriously polluted and the resource waste is caused.
Disclosure of Invention
The invention aims to provide a treatment method of gallium extraction waste liquid obtained after extracting aluminum and gallium from fly ash by an acid method, which can realize resource recycling of iron ions, aluminum ions and hydrochloric acid in the gallium extraction waste liquid, produce two different water purifying agents, and has no generation of secondary pollutants in the process, near zero emission and environmental protection.
The second purpose of the invention is to provide a polymeric ferric chloride water purifying agent and/or a polymeric aluminum chloride water purifying agent prepared by the treatment method.
In order to achieve the first purpose of the invention, the following technical scheme is adopted:
a treatment method of gallium extraction waste liquid obtained after extracting aluminum and gallium by a fly ash acid method is disclosed, wherein the gallium extraction waste liquid is obtained after extracting aluminum oxide and gallium by the fly ash acid method; the processing method comprises the following steps:
(1) separating and purifying the gallium extraction waste liquid to obtain ferric chloride solution and residual waste liquid;
(2) adding a polymerization agent into the ferric chloride solution obtained in the step (1) to carry out polymerization reaction; then standing and curing or drying the solution after the polymerization reaction to obtain a poly ferric chloride water purifying agent;
(3) adding fly ash into the residual waste liquid obtained in the step (1), uniformly mixing, then placing the mixture into a reaction kettle for reaction, cooling the slurry after the reaction, and performing solid-liquid separation to obtain a solid material and a liquid material;
(4) adding calcium aluminate into the liquid material obtained by separation in the step (3) to carry out polymerization reaction to obtain a polyaluminium chloride solution;
(5) and (4) drying the polyaluminium chloride solution obtained in the step (4) to obtain the polyaluminium chloride water purifying agent.
In the invention, the gallium extraction waste liquid is obtained after alumina and gallium are extracted from fly ash by an acid method, and the specific reference is made to the document "gallium recovery technology in acid system [ B ], Liu Yan Red and the like, light metals, 6 th stage in 2018, and 20-24. As can be seen from the description in paragraph 2 on the left column of fig. 1 and 20 in the above-mentioned document, the gallium extraction waste liquid refers to: in the process of extracting alumina from the fly ash by an acid method, the fly ash is separated and washed after being acid-dissolved by hydrochloric acid to obtain acid-leaching refined liquid; adsorbing iron and gallium in the acid leaching refined solution by using iron-removing resin; then eluting the adsorbed iron-removing resin by using 1-3% hydrochloric acid, and eluting iron and gallium in the adsorbed iron-removing resin to obtain iron-and-gallium-containing iron-removing resin eluent; then carrying out moderate evaporation concentration and filtration on the iron-removing resin eluent to obtain gallium-extracting stock solution; gallium in the gallium extracting raw liquid is adsorbed by gallium removing resin (according to the description of the right column 1 on page 20, gallium ions are preferably adsorbed by the gallium extracting resin), and the residual liquid after adsorption is the gallium extracting waste liquid. The fly ash includes, but is not limited to, fly ash from a circulating fluidized bed; preferably, the acid leaching refined solution is prepared by crushing the fly ash to be less than 100 meshes, performing wet magnetic separation to remove iron so that the content of iron oxide in the fly ash is reduced to be less than 1.0 wt%, then adding a hydrochloric acid solution into the fly ash for reaction and performing solid-liquid separation to obtain an acid leaching refined solution (also called hydrochloric acid leaching solution), for example, adding hydrochloric acid into the fly ash after iron removal, wherein aluminum, gallium, residual iron and other elements are dissolved out, and filtering insoluble residues to obtain the acid leaching refined solution (also called hydrochloric acid leaching solution).
In one embodiment, the gallium extraction waste liquid contains high concentration of iron ions, aluminum ions, hydrogen ions and a small amount of impurity ions (K)+、Na+、Ca2+、SiO2) The acid waste liquid is brownish red; e.g. Fe3+The content of Al is 60-110g/L, such as 70g/L, 80g/L, 90g/L or 100g/L3+The content is 20-60g/L, such as 30g/L, 40g/L or 50g/L, H+The content of the impurity ions is 0.5-5mol/L, such as 1mol/L, 2mol/L, 3mol/L or 4mol/L, and the sum of the contents of the other ions (which can be regarded as impurity ions) does not exceed 3.5g/L, such as 3g/L, and the impurity ions do not substantially influence the preparation of the poly-ferric chloride water purifying agent and/or the poly-aluminum chloride water purifying agent.
The treatment method can realize resource recycling of iron ions and aluminum ions in the gallium extraction waste liquid to obtain the poly-ferric chloride water purifying agent and the poly-aluminum chloride water purifying agent; in the process of recycling the aluminum, the hydrochloric acid in the aluminum is also utilized, so that the resource recycling of the hydrochloric acid is realized; and no secondary pollutant is generated in the treatment process, so that near zero emission and environmental protection can be realized. Wherein, the step (2) can realize the resource recycling of iron and simultaneously obtain the polyferric chloride water purifying agent; the steps (3) to (5) can realize resource recycling of aluminum and obtain a polyaluminium chloride water purifying agent at the same time; in the step (3), when the fly ash is added, hydrochloric acid in the fly ash is used for reacting with the fly ash, so that the resource recycling of the hydrochloric acid is realized; meanwhile, in the step (3), the solid material obtained by solid-liquid separation is neutral, and the main component of the solid material is silicon dioxide, so that the solid material can be used for producing heat-insulating boards, wall materials, building fillers, adsorbing materials and the like, and further can be comprehensively utilized.
In the step (1), Fe is contained in the ferric chloride solution obtained by separation and purification3+The content of (A) is 80-110g/L, and the purity of ferric chloride is more than or equal to 99.9%.
Preferably, in the step (1), the separation and purification is performed by an extraction process.
Preferably, the extraction process comprises multistage extraction, multistage washing and multistage stripping in sequence. Wherein "multi-stage" means at least 2 stages.
Preferably, the extraction process comprises 4-7 stages of extraction, 2 stages of washing and 4-6 stages of back extraction in sequence.
Secondary octanol can be selected as an extracting agent in each stage of extraction, and the extraction phase ratio O/A (the volume ratio of the extracting agent to an extraction water phase (namely, the gallium extraction waste liquid)) is (2-5): 1; other suitable extractants, such as N235, N503, etc. may also be selected;
hydrochloric acid with the concentration of 10-12 wt% can be selected as a detergent for each washing, and other suitable detergents can also be selected; the washing phase ratio A/O (i.e. the volume ratio of the washing agent to the loaded organic phase) is (5-15): 1;
hydrochloric acid with pH of 1-2 can be used as stripping agent for each stage of stripping, and other suitable stripping agents can also be selected; the stripping phase ratio O/A (namely the volume ratio of the washed loaded organic phase to the stripping agent) is (2.5-5): 1.
The extraction process is as follows: extracting the gallium extraction waste liquid in an extraction section by using an extracting agent in multiple stages (such as 4-7 stages), wherein extraction residual liquid (namely, residual waste liquid) is an acidic solution mainly containing aluminum chloride; the extracted loaded organic phase enters a washing section, and after washing is carried out in multiple stages (such as 2 stages) by using a detergent, washing liquid enters the extraction section; carrying out multi-stage (such as 4-6 stages) back extraction on the washed loaded organic phase by using a back extractant to obtain an iron chloride solution; the organic phase after back extraction is a no-load organic phase and can continuously return to the extraction section for extraction.
The step (1) can also be separated and purified by other methods, for example, separation and purification by using resin.
Preferably, in the polymerization reaction of step (2), the reaction temperature is 80 to 110 ℃, preferably 85 to 105 ℃, such as 90 ℃, 95 ℃ or 100 ℃; the reaction time is 2-4h, preferably 2.5-3.5h, such as 3h, so that the polymerization degree and the polymerization rate of the polymerization reaction in the step (2) are improved, and the high-quality polyferric chloride water purifying agent is obtained.
Preferably, the polymerization reaction of the step (2) is carried out in a reaction kettle in a closed manner.
Preferably, in the step (2), the temperature for standing and curing is 80-90 ℃, such as 82 ℃, 84 ℃, 86 ℃ or 88 ℃; standing and curing for 24-48h, such as 28h, 30h, 34h, 38h, 40h or 44h, so as to allow the substances in the solution after the polymerization reaction to fully interact, thereby obtaining the stable polyferric chloride water purifying agent.
Preferably, in the step (2), the drying manner includes spray drying, and other drying manners, such as heat drying, are also possible.
In the step (2), the solution after the polymerization reaction is kept stand and cured to obtain the liquid polyferric chloride water purifying agent, and the liquid polyferric chloride water purifying agent is dried to obtain the solid polyferric chloride water purifying agent. The solid polyferric chloride water-purifying agent can also be obtained by drying the solid polyferric chloride water-purifying agent after standing and curing.
Preferably, in the step (2), the mass ratio of the polymerization agent to the ferric chloride in the ferric chloride solution is (0.001-0.01):1, preferably (0.003-0.009):1, such as 0.004:1, 0.005:1, 0.006:1, 0.007:1 or 0.008:1, so that the ferric chloride in the ferric chloride solution can be completely polymerized as much as possible, and the resource recycling of the iron ions in the gallium extraction waste liquid is realized.
Preferably, the polymerization agent comprises any one or combination of citric acid, acetic acid, silicic acid.
Preferably, in the step (3), the reaction temperature is 100-; the reaction time is 2-4h, preferably 2.5-3.5h, such as 3h, so as to facilitate the reaction of the hydrochloric acid and the fly ash to be better and faster.
Preferably, in the step (3), the mass ratio of the fly ash to the residual waste liquid is (0.05-0.2):1, preferably (0.07-0.18):1, such as 0.08:1, 0.09:1, 0.1:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.16:1 or 0.17:1, so that hydrochloric acid in the residual waste liquid is completely utilized to react with the fly ash to completely consume the hydrochloric acid therein, resource recycling of the hydrochloric acid therein is realized, and an intermediate material (i.e., the liquid material) for producing the polyaluminium chloride water purifying agent is generated.
Preferably, in the step (3), hydrochloric acid with a concentration of 28 to 32 wt% is added before the reaction, preferably with a concentration of 30 to 31.5 wt%, such as 30.5 wt% or 31 wt%, so that more reaction products can be produced, more solid materials and intermediate materials (i.e., the liquid materials) for producing the polyaluminum chloride water purifying agent can be obtained, and thus more polyaluminum chloride water purifying agent can be obtained.
Further preferably, the mass ratio of the hydrochloric acid to the fly ash added is (0.1-2):1, preferably (0.4-1.7):1, such as 0.6:1, 0.8:1, 1:1, 1.2:1, 1.4:1, or 1.6: 1.
Preferably, in the step (3), the solid-liquid separation is to perform plate-and-frame filter pressing on the cooled and cooled reacted slurry. Of course, other filtering methods can be adopted, such as adding a flocculating agent into the slurry after the reaction after cooling and temperature reduction for settling separation. The flocculating agent can be selected from flocculating agents commonly used in the field.
Preferably, in the step (3), after the slurry is cooled to a temperature lower than 100 ℃ after the reaction, solid-liquid separation is performed, for example, the temperature is reduced to 95 ℃ or 98 ℃.
Preferably, in the polymerization reaction of the step (4), the reaction temperature is 90-105 ℃, preferably 93-102 ℃, such as 95 ℃, 97 ℃ or 100 ℃; the reaction time is 0.5-2.5h, preferably 1-2h, such as 1.5h, so as to increase the polymerization degree and polymerization rate of the polymerization reaction in the step (4) and to obtain a high-quality polyaluminium chloride water purifying agent later.
In the step (4), the mass ratio of the calcium aluminate to the liquid material separated in the step (3) is preferably (0.01-0.02):1, preferably (0.013-0.018):1, for example, 0.014:1, 0.015:1 or 0.016:1, so that aluminum chloride in the aluminum chloride solution can be completely polymerized as much as possible, and the aluminum ions in the gallium extraction waste liquid can be recycled.
Preferably, in the step (5), the drying is to spray-dry the polyaluminium chloride solution obtained in the step (4), or to evaporate and concentrate the polyaluminium chloride solution obtained in the step (4) and then to heat and dry the solution to obtain the polyaluminium chloride water purifying agent. Other drying methods may be used. The polyaluminium chloride water purifying agent obtained after drying is solid polyaluminium chloride water purifying agent.
Or standing and curing the polyaluminium chloride solution obtained in the step (4) to obtain the liquid polyaluminium chloride water purifying agent.
Preferably, in the steps (2) to (4), the reaction materials are stirred uniformly and then reacted.
In order to achieve the second object of the present invention, the present invention also provides a water purifying agent of poly-ferric chloride and/or poly-aluminum chloride prepared by the above-mentioned treatment method.
The treatment method of the gallium extraction waste liquid obtained after extracting aluminum and gallium by the fly ash acid method and the polymeric ferric chloride water purifying agent and/or the polymeric aluminum chloride water purifying agent prepared by the treatment method have the following beneficial effects:
(1) the treatment method of the gallium extraction waste liquid obtained after the aluminum and the gallium are extracted by the fly ash acid method can realize the resource recycling of iron ions and aluminum ions in the gallium extraction waste liquid, avoid resource waste and simultaneously obtain the poly-ferric chloride water purifying agent and the poly-aluminum chloride water purifying agent; in the process of recycling the aluminum, the hydrochloric acid in the aluminum is also utilized, so that the resource recycling of the hydrochloric acid is realized; and no secondary pollutant is generated in the treatment process, so that near zero emission and environmental protection can be realized.
(2) The poly-ferric chloride water purifying agent prepared by the treatment method has extremely low impurity content (less than 1 wt%), high purity and can be applied to industries with requirements on introducing impurity ions during water purification, and the product quality meets the product quality requirements of the national standard 'Water purifying agent-ferric chloride' (GB 4482-93).
(3) The quality of the polyaluminum chloride water purifying agent prepared by the treatment method meets the product quality requirement of water treatment agent polyaluminum chloride (GB/T22627-.
Detailed Description
The technical solution and effects of the present invention will be further described below by way of specific embodiments. The following embodiments are merely illustrative of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
Example 1
The composition of gallium-extracting waste liquid 1 used in example 1(S1) is shown in table 1.
Main composition of gallium extraction waste liquor 1 used in Table 1S 1
| Composition of matter | Fe3+ | Al3+ | H+ | Ca2+ | SiO2 | K+ | Na+ |
| Content (wt.) | 92.17g/L | 40.00g/L | 3.00mol/L | 1.50g/L | 0.17g/L | 0.47g/L | 0.53g/L |
The treatment method comprises the following steps:
(1) separating and purifying gallium-extracting waste liquor 1 in an extraction process of 6-grade extraction (an extracting agent adopts sec-octanol, and the extraction phase ratio is 3.5:1) and 2-grade washing (a washing agent adopts a hydrochloric acid solution with the concentration of 10 wt%, and the washing phase ratio is 10:1) and 5-grade back extraction (a back extracting agent is a hydrochloric acid solution with the pH of 2, and the back extracting phase ratio is 3.3:1) to obtain an iron chloride solution and residual waste liquor;
the extraction process is as follows: the extraction agent and the extraction phase are adopted to sequentially carry out 6-stage extraction on the gallium extraction waste liquid 1 to obtain an acid solution (namely, residual waste liquid) mainly containing aluminum chloride and a loaded organic phase after extraction; then, sequentially carrying out 2-level washing on the extracted loaded organic phase by adopting the detergent and the washing phase to obtain washing liquid and the washed loaded organic phase; then, sequentially carrying out 5-stage back extraction on the washed loaded organic phase by adopting the back extractant and the back extraction phase to obtain an iron chloride solution and a no-load organic phase;
wherein the purity of ferric chloride in the obtained ferric chloride solution is 99.94 percent, and Fe3+The content of (2) is 96.3g/L, and Fe in the residual waste liquid3+The content of (B) is 0.2g/L, Al3+The content of (B) is 42.1g/L, H+The content of (A) is 3.5 g/L;
(2) adding citric acid into the ferric chloride solution obtained in the step (1), wherein the mass ratio of the added citric acid to the ferric chloride in the ferric chloride solution is 1:1000 (namely 0.001:1), uniformly stirring, and then placing the mixture into a closed reaction kettle for polymerization reaction at 95 ℃ for 2.5 hours; standing and curing the solution after the polymerization reaction at 90 ℃ for 36 hours to obtain a polyferric chloride water purifying agent;
(3) adding fly ash into the residual waste liquid obtained in the step (1), uniformly mixing, wherein the mass ratio of the added fly ash to the residual waste liquid is 1:5 (namely 0.2:1), then placing the mixture into a reaction kettle, reacting for 2.5 hours at 150 ℃, cooling the slurry after reaction to 95 ℃, performing plate-frame filter pressing, and washing to realize solid-liquid separation to obtain a solid material and a liquid material;
(4) adding calcium aluminate into the liquid material obtained by separation in the step (3), wherein the mass ratio of the calcium aluminate to the liquid material obtained by separation in the step (3) is 3:200 (namely 0.015:1), uniformly stirring, and carrying out polymerization reaction for 1.5h at 100 ℃ to obtain a polyaluminium chloride solution;
(5) and (4) spray drying the polyaluminium chloride solution obtained in the step (4) to obtain powder, namely the solid polyaluminium chloride water purifying agent.
As a result:
the poly ferric chloride water purifying agent product obtained in the step (2) has extremely low impurity content (the content of impurity ions is less than 1 wt%), the product quality meets the product quality requirement of the national standard 'water purifying agent ferric chloride' (GB 4482-93), and the poly ferric chloride water purifying agent product can be applied to the industry requiring the introduction of impurity ions in water purification;
the solid material obtained in the step (3) mainly comprises SiO2And undiluted alumina in an amount of about 70 wt% and 18 wt%, respectively, the solid waste being either recycled or subjected to lime-addition harmless treatment and stockpiled;
the product quality of the solid polyaluminium chloride water purifying agent obtained in the step (5) meets the product quality requirement of water treatment agent polyaluminium chloride (GB/T22627-2014).
Example 2
The composition of the gallium-extracting waste liquid 2 used in example 2(S2) is shown in table 2.
Main composition of gallium extraction waste liquid 2 used in Table 2S 2
| Composition of matter | Fe3+ | Al3+ | H+ | Ca2+ | SiO2 | K+ | Na+ |
| Content (wt.) | 98.32g/L | 23.50g/L | 3.40mol/L | 2.10g/L | 0.12g/L | 0.43g/L | 0.48g/L |
The treatment method comprises the following steps:
(1) separating and purifying gallium extraction waste liquid 2 in the meter 2 by adopting an extraction process of 7-grade extraction (N235 is adopted as an extracting agent, and the ratio of extraction to O/A is 5:1) + 2-grade washing (12 wt% hydrochloric acid solution is adopted as a washing agent, and the ratio of washing to O/A is 15:1) + 6-grade back extraction (the ratio of back extraction to O/A is 5:1 hydrochloric acid solution is adopted as a back extraction agent), so as to obtain an iron chloride solution and residual waste liquid;
the extraction process is as follows: the extraction agent and the extraction phase are adopted to sequentially perform 7-stage extraction on the gallium extraction waste liquid 2 to obtain an acid solution (namely, residual waste liquid) mainly containing aluminum chloride and a loaded organic phase after extraction; then, sequentially carrying out 2-level washing on the extracted loaded organic phase by adopting the detergent and the washing phase to obtain washing liquid and the washed loaded organic phase; then, sequentially carrying out 6-stage back extraction on the washed loaded organic phase by adopting the back extractant and the back extraction phase to obtain an iron chloride solution and a no-load organic phase;
wherein the purity of ferric chloride in the obtained ferric chloride solution is 99.97 percent, and the purity of Fe3+The content of (2) is 104.2g/L, and Fe in the residual waste liquid3+The content of (B) is 0.3g/L, Al3+The content of (B) is 24.8g/L, H+The content of (A) is 3.7 g/L;
(2) adding acetic acid into the ferric chloride solution obtained in the step (1), wherein the mass ratio of the added acetic acid to the ferric chloride in the ferric chloride solution is 9:1000 (namely 0.009:1), uniformly stirring, and then placing the mixture into a closed reaction kettle for polymerization reaction at 80 ℃ for 4 hours; heating and drying the solution after the polymerization reaction to obtain a polyferric chloride water purifying agent;
(3) adding fly ash into the residual waste liquid obtained in the step (1), uniformly mixing, wherein the mass ratio of the added fly ash to the residual waste liquid is 1:10 (namely 0.1:1), then placing the mixture into a reaction kettle, reacting for 4 hours at 100 ℃, cooling the slurry after reaction to 95 ℃, performing plate-frame filter pressing, and washing to realize solid-liquid separation to obtain a solid material and a liquid material;
(4) adding calcium aluminate into the liquid material obtained by separation in the step (3), wherein the mass ratio of the calcium aluminate to the liquid material obtained by separation in the step (3) is 1:50 (namely 0.02:1), uniformly stirring, and carrying out polymerization reaction at 105 ℃ for 0.5h to obtain a polyaluminium chloride solution;
(5) and (4) spray drying the polyaluminium chloride solution obtained in the step (4) to obtain powder, namely the solid polyaluminium chloride water purifying agent.
As a result:
the poly ferric chloride water purifying agent product obtained in the step (2) has extremely low impurity content (the content of impurity ions is less than 1 wt%), the product quality meets the product quality requirement of the national standard 'water purifying agent ferric chloride' (GB 4482-93), and the poly ferric chloride water purifying agent product can be applied to the industry requiring the introduction of impurity ions in water purification;
the solid material obtained in the step (3) mainly comprises SiO2And undiluted alumina in an amount of about 75 wt% and 13 wt%, respectively, the solid waste being either recycled or subjected to lime-addition harmless treatment and stockpiled;
the product quality of the solid polyaluminium chloride water purifying agent obtained in the step (5) meets the product quality requirement of water treatment agent polyaluminium chloride (GB/T22627-2014).
Example 3
The composition of gallium-extracting waste liquid 3 used in example 3(S3) is shown in table 3.
Main composition of gallium extraction waste liquor 3 used in Table 3S 3
| Composition of matter | Fe3+ | Al3+ | H+ | Ca2+ | SiO2 | K+ | Na+ |
| Content (wt.) | 75.50g/L | 55.36g/L | 2.0mol/L | 1.85g/L | 0.26g/L | 0.38g/L | 0.42g/L |
The treatment method comprises the following steps:
(1) separating and purifying gallium extraction waste liquid 3 in the table 3 by adopting an extraction process of 4-grade extraction (N503 is adopted as an extraction agent, and the extraction phase ratio is 2:1) + 2-grade washing (11% hydrochloric acid solution is adopted as a washing agent, and the washing phase ratio is 5:1) + 5-grade back extraction (the back extraction agent is hydrochloric acid solution with the pH value of 1.5, and the back extraction phase ratio is 2.5:1) to obtain ferric chloride solution and residual waste liquid;
the extraction process is as follows: the extraction agent and the extraction phase are adopted to sequentially perform 4-stage extraction on the gallium extraction waste liquid 3 to obtain an acid solution (namely, residual waste liquid) mainly containing aluminum chloride and a loaded organic phase after extraction; then, sequentially carrying out 2-level washing on the extracted loaded organic phase by adopting the detergent and the washing phase to obtain washing liquid and the washed loaded organic phase; then, sequentially carrying out 5-stage back extraction on the washed loaded organic phase by adopting the back extractant and the back extraction phase to obtain an iron chloride solution and a no-load organic phase;
wherein the purity of ferric chloride in the obtained ferric chloride solution is 99.91 percent, and Fe3+The content of (2) is 85.1g/L, and Fe in the residual waste liquid3+Has a content of 0.082g/L and Al3+Has a content of 58.65g/L, H+The content of (A) is 2.1 g/L;
(2) adding silicic acid into the ferric chloride solution obtained in the step (1), wherein the mass ratio of the added silicic acid to the ferric chloride in the ferric chloride solution is 1:125 (namely 0.008:1), uniformly stirring, and then placing the mixture into a closed reaction kettle for polymerization reaction at 110 ℃ for 2 hours; heating and drying the solution after the polymerization reaction to obtain a polyferric chloride water purifying agent;
(3) adding fly ash into the residual waste liquid obtained in the step (1) and uniformly mixing, wherein the mass ratio of the added fly ash to the residual waste liquid is 1:20 (namely 0.05: 1); adding 31 wt% hydrochloric acid, wherein the mass ratio of the added hydrochloric acid to the fly ash is 1:5 (namely 0.2: 1); then, placing the uniformly mixed slurry into a reaction kettle to react for 2.0 hours at 160 ℃, cooling the slurry after the reaction to 95 ℃, then performing plate-frame filter pressing, and washing to realize solid-liquid separation to obtain a solid material and a liquid material;
(4) adding calcium aluminate into the liquid material obtained by separation in the step (3), wherein the mass ratio of the calcium aluminate to the liquid material obtained by separation in the step (3) is 1:100 (namely 0.01:1), uniformly stirring, and carrying out polymerization reaction at 90 ℃ for 2.5h to obtain a polyaluminium chloride solution;
(5) and (4) spray drying the polyaluminium chloride solution obtained in the step (4) to obtain powder, namely the solid polyaluminium chloride water purifying agent.
As a result:
the poly ferric chloride water purifying agent product obtained in the step (2) has extremely low impurity content (the content of impurity ions is less than 1 wt%), the product quality meets the product quality requirement of the national standard 'water purifying agent ferric chloride' (GB 4482-93), and the poly ferric chloride water purifying agent product can be applied to the industry requiring the introduction of impurity ions in water purification;
the solid material obtained in the step (3) mainly comprises SiO2And undiluted alumina in an amount of about 68 wt% and 20 wt%, respectively, the solid waste being either recycled or subjected to lime-addition harmless treatment and stockpiled;
the product quality of the solid polyaluminium chloride water purifying agent obtained in the step (5) meets the product quality requirement of water treatment agent polyaluminium chloride (GB/T22627-2014).
According to the embodiments 1-3 and the results thereof, the treatment method of the gallium extraction waste liquid obtained after extracting aluminum and gallium by the fly ash acid method can recycle the iron ions and the aluminum ions in the gallium extraction waste liquid, avoid resource waste, and simultaneously obtain two different water purifying agents, namely a polyferric chloride water purifying agent and a polyaluminum chloride water purifying agent, thereby creating certain economic benefits; and no secondary pollutant is generated in the treatment process, near zero emission can be realized, and the problem of environmental protection treatment of the wastewater is thoroughly solved.
Claims (10)
1. A treatment method of gallium extraction waste liquid obtained after extracting aluminum and gallium by a fly ash acid method is characterized in that the gallium extraction waste liquid is obtained after extracting aluminum oxide and gallium by the fly ash acid method; the processing method comprises the following steps:
(1) separating and purifying the gallium extraction waste liquid to obtain ferric chloride solution and residual waste liquid;
(2) adding a polymerization agent into the ferric chloride solution obtained in the step (1) to carry out polymerization reaction; then standing and curing or drying the solution after the polymerization reaction to obtain a poly ferric chloride water purifying agent;
(3) adding fly ash into the residual waste liquid obtained in the step (1), uniformly mixing, then placing the mixture into a reaction kettle for reaction, cooling the slurry after the reaction, and performing solid-liquid separation to obtain a solid material and a liquid material;
(4) adding calcium aluminate into the liquid material obtained by separation in the step (3) to carry out polymerization reaction to obtain a polyaluminium chloride solution;
(5) and (4) drying the polyaluminium chloride solution obtained in the step (4) to obtain the polyaluminium chloride water purifying agent.
2. The process according to claim 1, wherein the polymerization reaction in step (2) is carried out at a reaction temperature of 80 to 110 ℃ for a reaction time of 2 to 4 hours.
3. The process according to claim 1 or 2, wherein in the step (2), the temperature for standing and curing is 80-90 ℃ and the time is 24-48 h.
4. The process according to any one of claims 1 to 3, wherein in the step (2), the mass ratio of the polymerizing agent to the ferric chloride in the ferric chloride solution is (0.001-0.01): 1;
preferably, the polymerization agent comprises any one or combination of citric acid, acetic acid, silicic acid.
5. The process according to any one of claims 1 to 4, wherein in the step (3), the reaction temperature is 100 ℃ and the reaction time is 2 to 4 hours.
6. The treatment method according to any one of claims 1 to 5, wherein in the step (3), the mass ratio of the fly ash to the remaining waste liquid is (0.05-0.2): 1.
7. The process according to any one of claims 1 to 6, wherein in the step (3), hydrochloric acid having a concentration of 28 to 32% by weight is added before the reaction;
preferably, the mass ratio of the added hydrochloric acid to the fly ash is (0.1-2): 1.
8. The process according to any one of claims 1 to 7, wherein the polymerization reaction in step (4) is carried out at a reaction temperature of 90 to 105 ℃ for a reaction time of 0.5 to 2.5 hours.
9. The process according to any one of claims 1 to 8, wherein in step (4), the mass ratio of the calcium aluminate to the liquid material separated in step (3) is (0.01-0.02): 1.
10. A water purifying agent of polymeric ferric chloride and/or polymeric aluminum chloride prepared by the treatment method of any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314623A (en) * | 2020-09-30 | 2022-04-12 | 中国科学院过程工程研究所 | Method for producing metallurgical-grade aluminum oxide by using refined aluminum chloride solution |
| CN114573035A (en) * | 2022-03-03 | 2022-06-03 | 神华准能资源综合开发有限公司 | Method for preparing polyaluminum ferric chloride from gallium extraction waste liquid by one-step acid dissolution method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915852A (en) * | 2006-08-30 | 2007-02-21 | 吉林大学 | Aluminum chlorate of polymerized silicic acid and preparation method |
| CN108033490A (en) * | 2017-12-12 | 2018-05-15 | 青岛市昌斯达环保科技有限公司 | A kind of production method and technique of high-performance poly-ferric chloride |
-
2019
- 2019-11-08 CN CN201911085837.XA patent/CN110713199A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915852A (en) * | 2006-08-30 | 2007-02-21 | 吉林大学 | Aluminum chlorate of polymerized silicic acid and preparation method |
| CN108033490A (en) * | 2017-12-12 | 2018-05-15 | 青岛市昌斯达环保科技有限公司 | A kind of production method and technique of high-performance poly-ferric chloride |
Non-Patent Citations (1)
| Title |
|---|
| 姬学良等: ""高铝粉煤灰盐酸法生产氧化铝废水处理技术研究"", 《世界有色金属》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314623A (en) * | 2020-09-30 | 2022-04-12 | 中国科学院过程工程研究所 | Method for producing metallurgical-grade aluminum oxide by using refined aluminum chloride solution |
| CN114573035A (en) * | 2022-03-03 | 2022-06-03 | 神华准能资源综合开发有限公司 | Method for preparing polyaluminum ferric chloride from gallium extraction waste liquid by one-step acid dissolution method |
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