CN110844897B - Treatment method of waste phosphoric acid on running water treatment line - Google Patents
Treatment method of waste phosphoric acid on running water treatment line Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/28—Ammonium phosphates
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention discloses a treatment method of a waste phosphoric acid flow treatment line, which is provided with two branches, wherein the two branches are used for respectively carrying out different treatments on the waste phosphoric acid so as to obtain two mixed liquids, then the two mixed liquids enter a crystallization kettle for mixed crystallization, and finally a centrifuge is used for carrying out fixed separation treatment so as to obtain monoammonium phosphate solid.
Description
Technical Field
The invention relates to a treatment method of a waste phosphoric acid flowing water treatment line.
Background
In an aluminum-based electrode etching section in the manufacturing process of a liquid crystal panel, and in an aluminum alloy interconnect wet etching section in the manufacturing process of a semiconductor, a large amount of phosphoric acid-nitric acid-acetic acid waste liquid (hereinafter referred to as "waste phosphoric acid") needs to be discharged. The typical composition ratio of the waste phosphoric acid tank liquor is 65-70% of phosphoric acid, 1-3% of nitric acid, 3-10% of acetic acid, 0.1-0.3% of aluminum ion and 15-25% of water. If the waste tank liquor is mixed with the washing wastewater, the concentration of phosphoric acid, acetic acid and nitric acid can be greatly reduced, but the content of available phosphorus (P2O 5) of the mixed waste phosphoric acid is usually not lower than 30g/L. Waste phosphoric acid belongs to dangerous waste, and has high acidity and strong corrosiveness. Once the waste phosphoric acid leaks into the water body, the water body can be eutrophicated, and the harm of the acid component to the environment is not negligible. Meanwhile, phosphorus is an essential element indispensable to life activities, and is an important natural resource and industrial and agricultural raw material which are not renewable and are in face of exhaustion. Therefore, development of waste phosphoric acid treatment and utilization technology is attracting attention.
Currently, there are three types of treatment routes for waste phosphoric acid. The first is classical physicochemical precipitation. Because the main hazard of waste phosphoric acid is acid corrosiveness, phosphorus-containing and other biological nutrient substances, the hazard can be solved by adopting a way of neutralizing and precipitating by adding excessive alkaline substances such as lime, magnesium oxide and the like at one time. The generated sludge has qualified content of effective phosphorus and can be used as phosphate fertilizer, otherwise, the sludge is required to be sent to a professional institution for landfill; the filtrate is subjected to deep dephosphorization treatment and then discharged after reaching the standard. The method has mature technology and simple and reliable operation. However, the sludge has high water content, low effective phosphorus content and low fertilizer value, and can be only used for landfill treatment, so that the phosphorus resource is extremely wasted. The second type is the recycling method. Chinese patents CN1781842a and CN102167415A describe a method for incompletely regenerating waste phosphoric acid, in which a mixed solution of trialkyl phosphate and aliphatic linear saturated hydrocarbon having 6_13 carbon atoms is used to selectively extract and separate acetic acid and nitric acid from the waste phosphoric acid, and then the mixed solution is back-extracted with alkali metal or alkaline earth metal chloride solution, wherein the acetic acid and nitric acid in the back-extracted solution can be used to prepare new etching solution; however, the use of phosphoric acid in the raffinate is not further elucidated. While Chinese patent CN102421703A describes another incomplete regeneration method of waste phosphoric acid, which adds calcium hydroxide or calcium carbonate to waste phosphoric acid to pH 4 to precipitate calcium hydrogen phosphate from phosphoric acid and separate the calcium hydrogen phosphate from waste liquid; washing and removing impurities on the surface of the calcium hydrophosphate, and then reacting with sulfuric acid to generate phosphoric acid and calcium sulfate; separating and removing coarse phosphoric acid after calcium sulfate, purifying by adopting methods such as ion exchange adsorption, melt crystallization and the like, and finally obtaining electronic grade phosphoric acid which can be used for preparing an etching agent of a liquid crystal panel; however, the method avoids the treatment or utilization mode of acetic acid and nitric acid in the waste phosphoric acid. The third category is comprehensive utilization. Chinese patent CN101439849a describes a method for comprehensively utilizing waste phosphoric acid, in which acetic acid and nitric acid are separated from waste phosphoric acid by distillation, and industrial grade 85% phosphoric acid is obtained after filtering the distillation raffinate to remove mechanical impurities and adding water to adjust the phosphoric acid content; the distilled acetic acid and nitric acid are neutralized by caustic soda, and concentrated and crystallized in steps to obtain sodium acetate and sodium nitrate. Chinese patent CN102139975a describes another method for comprehensively utilizing waste phosphoric acid by adding a magnesium source and a nitrogen source to the waste phosphoric acid, controlling pH of the waste liquid, adjusting molar ratio of magnesium salt, ammonia nitrogen and phosphate in the waste liquid, heating the waste liquid to precipitate phosphorus in the waste liquid as magnesium ammonium phosphate, and separating and utilizing phosphorus in the waste phosphoric acid, but there is no further description of treatment or utilization of acetic acid and nitric acid in the waste phosphoric acid. The agricultural production in China has great demands on nitrogen and phosphorus fertilizers, and phosphoric acid and nitric acid components in waste phosphoric acid are good fertilizer resources. On the other hand, acetate ions in waste phosphoric acid are easily degraded by soil microorganisms, and few reports about the interference of acetate on plant growth are provided. In addition, in the acid-base neutralization process, aluminum ions with low concentration in the waste phosphoric acid firstly generate aluminum hydroxide gel and are gradually converted into inert aluminum hydroxide, so that the waste phosphoric acid does not have any harm to crops; also, low concentrations of water insoluble aluminum hydroxide or aluminum oxyhydroxide have little effect on the water insoluble content index of the fertilizer.
In the above-mentioned methods for treating waste phosphoric acid, the waste phosphoric acid is not recycled well, and the utilization rate is low, and the treatment process is complicated, so how to overcome the above-mentioned defects is an important problem to be solved by those skilled in the art.
Disclosure of Invention
The invention overcomes the defects of the technology and provides a method for treating waste phosphoric acid by using a running water treatment line.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for treating waste phosphoric acid comprises the following steps:
step A, taking a part of waste phosphoric acid, adding ammonia water into the waste phosphoric acid, regulating the pH value to be in a range of 5.3-5.5 to obtain a first solid-liquid mixture, then carrying out solid-liquid separation treatment on the first solid-liquid mixture to obtain a first mixed solution containing diammonium phosphate and a first filter residue containing aluminum hydroxide and aluminum hydrogen phosphate, and then concentrating the first mixed solution to obtain a first concentrated solution;
step B, taking a part of waste phosphoric acid, adding ammonia water into the waste phosphoric acid, regulating the pH value to be in a range of 4.1-4.3 to obtain a second solid-liquid mixture, then carrying out solid-liquid separation treatment on the second solid-liquid mixture to obtain a second mixed solution containing phosphoric acid, monoammonium phosphate and aluminum ions and a second filter residue containing aluminum dihydrogen phosphate, then allowing the second mixed solution to enter an ion exchange system, and adsorbing the aluminum ions in the second mixed solution by using aluminum ion exchange resin to obtain a third mixed solution containing monoammonium phosphate and phosphoric acid;
and C, gradually adding the third mixed solution obtained in the step B into the first concentrated solution obtained in the step A, adjusting the pH value to be in a range of 4.3-4.5, crystallizing, and then carrying out solid-liquid separation treatment to obtain monoammonium phosphate solid and separating liquid.
In the method for treating the waste phosphoric acid, when the waste phosphoric acid is used in the step A and the step B, the waste phosphoric acid with lower phosphoric acid content is treated in the step A, and the waste phosphoric acid with higher phosphoric acid content is treated in the step B.
In the method for treating the waste phosphoric acid, when the waste phosphoric acid is taken in the step A and the step B, the waste phosphoric acid with the phosphoric acid content of less than 30% is treated in the step A, and the waste phosphoric acid with the phosphoric acid content of not less than 30% is treated in the step B.
In the above-described method for treating waste phosphoric acid, the concentration of ammonia water used in the step A and the step B is 25% or more.
In the method for treating waste phosphoric acid, in the step A, when the first mixed solution is concentrated, the effective phosphorus content of the concentrated solution is controlled to be in the range of 250-300 g/L.
The method for treating the waste phosphoric acid further comprises a step D, wherein the separation liquid obtained after the solid-liquid separation in the step C is returned to the crystallization process in the step C for recycling.
In the method for treating waste phosphoric acid as described above, the first residue obtained in the step A and the second residue obtained in the step B are treated as industrial solid waste.
As described above, the present application also protects a waste phosphoric acid treatment line, which comprises a first reaction kettle 1 for allowing a part of waste phosphoric acid and ammonia water to react therein to obtain a first solid-liquid mixture, a first filter press 2 for performing a solid-liquid separation treatment on the first solid-liquid mixture output from the first reaction kettle 1 to obtain a first mixed solution and a first filter residue, a concentrating device 3 for concentrating the first mixed solution output from the first filter press 2 to obtain a first concentrated solution, a crystallization kettle 4 for storing the first concentrated solution output from the concentrating device 3, a second reaction kettle 5 for allowing a part of waste phosphoric acid and ammonia water to react therein to obtain a second solid-liquid mixture, a second filter press 6 for performing a solid-liquid separation treatment on the second solid-liquid mixture output from the second reaction kettle 5 to obtain a second mixed solution and a second filter residue, an ion exchange system 7 for adsorbing aluminum ions in the second mixed solution by an ion exchange resin to obtain a third mixed solution, a storage container 8 for storing the third mixed solution, a controlled crystallization kettle 4 for controlling the storage of the third mixed solution, and a controlled conveyance of the third mixed solution to the crystallization kettle 8 to the crystallization kettle 4 for controlling the controlled conveyance of the third mixed solution to be subjected to a controlled centrifuge.
In the above-mentioned waste phosphoric acid flow line, the separated liquid from the centrifuge 10 is returned to the crystallization kettle 4 through a pipe.
Compared with the prior art, the invention has the beneficial effects that:
1. the method for treating the waste phosphoric acid comprises the steps of carrying out different treatments on the waste phosphoric acid in the step A and the step B to obtain a first mixed solution and a second mixed solution, so that the two mixed solutions are mixed in the step C and then are subjected to crystallization treatment to obtain monoammonium phosphate solid, and the method has good innovation, wherein ammonia water is added into the waste phosphoric acid in the step A, the pH value is regulated to be in the range of 5.3-5.5, and aluminum ions in the waste phosphoric acid are conveniently treated by aluminum hydroxide Al (OH) 3 And aluminum hydrogen phosphate (Al) 2 (HPO 4 ) 3 Precipitating, and removing aluminum hydroxide Al (OH) by solid-liquid separation 3 And aluminum hydrogen phosphate (Al) 2 (HPO 4 ) 3 The first mixed solution containing the diammonium phosphate is obtained after precipitation, and then the concentration treatment is carried out, so that the content of effective phosphorus is improved; in the step B, ammonia water is added into the waste phosphoric acid, and the pH value is regulated to be in the range of 4.1-4.3, so that the aluminum ions in the waste phosphoric acid can be partially generated into colloidal Al (H) 2 PO 4 ) 3 Removing most of aluminum ions through solid-liquid separation treatment to obtain a second mixed solution containing phosphoric acid, monoammonium phosphate and aluminum ions, and adsorbing the rest aluminum ions in the second mixed solution through an ion exchange system to obtain a third mixed solution containing monoammonium phosphate and phosphoric acid; in the step C, the third mixed solution obtained in the step B is gradually added into the first concentrated solution obtained in the step A, the pH value is regulated to be in the range of 4.3-4.5, and crystallization is carried out, so that monoammonium phosphate NH is better used in the mixed solution 4 H 2 PO 4 Crystallization and reduction of diammonium phosphate (NH) 4 ) 2 HPO 4 So that it is advantageous on the one hand for increasing the phosphorus content of the crystals and on the other hand for reducing the NH 4 + To facilitate cost saving and monoammonium phosphate NH in crystallization kettle 4 H 2 PO 4 Continuously crystallizing, and performing solid-liquid separation after crystallization to obtain monoammonium phosphate NH 4 H 2 PO 4 The solid can be used for manufacturing fertilizer, and has good practicability.
2. The pH value of the waste phosphoric acid in the step A is adjusted to be in a range of 5.3-5.5 by adding ammonia water, and the pH value of the waste phosphoric acid in the step B is adjusted to be in a range of 4.1-4.3 by adding ammonia water, so that if the step A treatment is carried out on the waste phosphoric acid with relatively more phosphoric acid content, phosphate is easily entrained in filter residues, a large amount of phosphorus resources are lost, the step A treatment is carried out on the waste phosphoric acid with less phosphoric acid content, and the loss control of the phosphorus resources and the control of the concentration cost are facilitated; if the step B treatment is carried out on the waste phosphoric acid with relatively low phosphoric acid content, the concentration of phosphoric acid is too low, more monoammonium phosphate crystals are generated when the step C is not carried out, on the other hand, the content of aluminum ions in the waste phosphoric acid with low phosphoric acid content is higher, the load of an ion exchange system is easily caused to be too high because of higher content of aluminum ions, and if unclean aluminum elements are removed, the obtained product has too high relative impurity content, the step B treatment is carried out on the waste phosphoric acid with high phosphoric acid content, the high efficiency of utilizing the ion exchange system is facilitated, and meanwhile, the damage of the ion exchange system is avoided.
3. In the scheme, when the first mixed solution is concentrated in the step A, the effective phosphorus content of the concentrated solution is controlled to be in the range of 250-300 g/L, so that the first concentrated solution is not easy to crystallize in the concentrating process, and the effective phosphorus content is properly increased to be beneficial to easier crystallization in the step C.
4. The flow line of the waste phosphoric acid is provided with two branches, the waste phosphoric acid is respectively treated differently so as to obtain two mixed liquids, then the two mixed liquids enter a crystallization kettle for mixed crystallization, and finally the mixed liquids are subjected to fixed separation treatment by a centrifuge so as to obtain monoammonium phosphate solid.
Drawings
Fig. 1 is a schematic structural diagram of the present case.
Detailed Description
The following examples are provided to illustrate the features of the present invention and other related features in further detail to facilitate understanding by those skilled in the art:
as shown in FIG. 1, the method for treating the waste phosphoric acid is characterized by comprising the following steps:
step A, taking a part of waste phosphoric acid, adding ammonia water into the waste phosphoric acid, regulating the pH value to be in a range of 5.3-5.5 to obtain a first solid-liquid mixture, then carrying out solid-liquid separation treatment on the first solid-liquid mixture to obtain a first mixed solution containing diammonium phosphate and a first filter residue containing aluminum hydroxide and aluminum hydrogen phosphate, and then concentrating the first mixed solution to obtain a first concentrated solution;
step B, taking a part of waste phosphoric acid, adding ammonia water into the waste phosphoric acid, regulating the pH value to be in a range of 4.1-4.3 to obtain a second solid-liquid mixture, then carrying out solid-liquid separation treatment on the second solid-liquid mixture to obtain a second mixed solution containing phosphoric acid, monoammonium phosphate and aluminum ions and a second filter residue containing aluminum dihydrogen phosphate, then allowing the second mixed solution to enter an ion exchange system, and adsorbing the aluminum ions in the second mixed solution by using aluminum ion exchange resin to obtain a third mixed solution containing monoammonium phosphate and phosphoric acid;
and C, gradually adding the third mixed solution obtained in the step B into the first concentrated solution obtained in the step A, adjusting the pH value to be in a range of 4.3-4.5, crystallizing, and then carrying out solid-liquid separation treatment to obtain monoammonium phosphate solid and separating liquid.
As described above, the method for treating waste phosphoric acid according to the present invention comprises the steps of A and B, wherein in step A, ammonia water is added to waste phosphoric acid, and pH is adjusted to a range of 5.3-5.5, so that aluminum ions in waste phosphoric acid can be treated as aluminum hydroxide Al (OH), and in step C, the waste phosphoric acid is treated differently to obtain a first mixed solution and a second mixed solution, and then the two mixed solutions are mixed and crystallized to obtain monoammonium phosphate solid 3 And aluminum hydrogen phosphate (Al) 2 (HPO 4 ) 3 Precipitating, and removing aluminum hydroxide Al (OH) by solid-liquid separation 3 And aluminum hydrogen phosphate (Al) 2 (HPO 4 ) 3 The first mixed solution containing the diammonium phosphate is obtained after precipitation, and then the concentration treatment is carried out, so that the content of effective phosphorus is improved; in the step B, ammonia water is added into the waste phosphoric acid, and the pH value is regulated to be in the range of 4.1-4.3, so that the aluminum ions in the waste phosphoric acid can be partially generated into colloidal Al (H) 2 PO 4 ) 3 Removing most of aluminum ions through solid-liquid separation treatment to obtain a second mixed solution containing phosphoric acid, monoammonium phosphate and aluminum ions, and adsorbing the rest aluminum ions in the second mixed solution through an ion exchange system to obtain a third mixed solution containing monoammonium phosphate and phosphoric acid; in the step C, the third mixed solution obtained in the step B is gradually added into the first concentrated solution obtained in the step A, the pH value is regulated to be in the range of 4.3-4.5, and crystallization is carried out, so that monoammonium phosphate NH is better used in the mixed solution 4 H 2 PO 4 Crystallization and reduction of diammonium phosphate (NH) 4 ) 2 HPO 4 So that it is advantageous on the one hand for increasing the phosphorus content of the crystals and on the other hand for reducing the NH 4 + To facilitate cost saving and monoammonium phosphate NH in crystallization kettle 4 H 2 PO 4 Continuously crystallizing, and performing solid-liquid separation after crystallization to obtain monoammonium phosphate NH 4 H 2 PO 4 The solid can be used for manufacturing fertilizer, and has good practicability.
As described above, in the crystallization in the step C, cooling and stirring are performed for better crystallization.
As described above, in the specific implementation, when the waste phosphoric acid is taken in the step A and the step B, the waste phosphoric acid with relatively low effective phosphorus content is subjected to the step A treatment, and the waste phosphoric acid with relatively high effective phosphorus content is subjected to the step B treatment.
As described above, the pH value of the waste phosphoric acid in the step A is adjusted to the range of 5.3-5.5 by adding ammonia water, and the pH value of the waste phosphoric acid in the step B is adjusted to the range of 4.1-4.3 by adding ammonia water, so that if the step A treatment is carried out on the waste phosphoric acid with relatively more phosphoric acid content, phosphate is easy to be entrained in filter residues, a large amount of phosphorus resources are lost, the step A treatment is carried out on the waste phosphoric acid with less phosphoric acid content, and the loss control of the phosphorus resources and the control of the concentration cost are facilitated; if the step B treatment is carried out on the waste phosphoric acid with relatively low phosphoric acid content, the concentration of phosphoric acid is too low, more monoammonium phosphate crystals are generated when the step C is not carried out, on the other hand, the content of aluminum ions in the waste phosphoric acid with low phosphoric acid content is higher, the load of an ion exchange system is easily caused to be too high because of higher content of aluminum ions, and if unclean aluminum elements are removed, the obtained product has too high relative impurity content, the step B treatment is carried out on the waste phosphoric acid with high phosphoric acid content, the high efficiency of utilizing the ion exchange system is facilitated, and meanwhile, the damage of the ion exchange system is avoided.
As described above, in the concrete implementation, when waste phosphoric acid is taken in the step A and the step B, the waste phosphoric acid with the effective phosphoric acid content higher than 30% is subjected to the step A treatment, and the waste phosphoric acid with the phosphoric acid content lower than 30% is subjected to the step B treatment.
As described above, in the embodiment, the concentration of ammonia water used in the step A and the step B is 25% or more so as to reduce the addition of water.
As described above, in the embodiment, in the step A, when the first mixed solution is concentrated, the effective phosphorus content of the concentrated solution is controlled to be in the range of 250-300 g/L, which makes the first concentrated solution not easy to crystallize in the concentrating process, and on the other hand, properly increasing the effective phosphorus content is beneficial to easier crystallization in the step C.
As described above, in the embodiment, the method further comprises a step D, wherein the separation liquid obtained after the solid-liquid separation in the step C is returned to the crystallization process in the step C for recycling, i.e. the monoammonium phosphate solution remained after the monoammonium phosphate solid is separated is returned to the crystallization process in the step C for recycling, which is beneficial to improving the utilization rate.
As described above, in practice, the first residue obtained in step a and the second residue obtained in step B are treated as industrial solid waste.
As described above, the present disclosure further discloses a waste phosphoric acid treatment line, which includes a first reaction kettle 1 for reacting a part of waste phosphoric acid and ammonia water therein to obtain a first solid-liquid mixture, a second filter press 2 for performing a solid-liquid separation treatment on the first solid-liquid mixture output from the first reaction kettle 1 to obtain a first mixed solution and a first filter residue, a concentrating device 3 for concentrating the first mixed solution output from the first filter press 2 to obtain a first concentrated solution, a crystallization kettle 4 for storing the first concentrated solution output from the concentrating device 3, a second reaction kettle 5 for reacting a part of waste phosphoric acid and ammonia water therein to obtain a second solid-liquid mixture, a second filter press 6 for performing a solid-liquid separation treatment on the second solid-liquid mixture output from the second reaction kettle 5 to obtain a second mixed solution and a second filter residue, an ion exchange system 7 for adsorbing aluminum ions in the second mixed solution by ion exchange resin to obtain a third mixed solution, a storage container 8 for storing the third mixed solution, a controlled crystallization kettle 4 for controlling the storage container 8 and a controlled conveyance of the third mixed solution to the crystallization kettle 4 for a controlled conveyance of the third mixed solution to the crystallization kettle 4.
As described above, the flow line for the waste phosphoric acid in the present case has two branches, which respectively carry out different treatments on the waste phosphoric acid so as to obtain two mixed liquids, then the two mixed liquids enter the crystallization kettle 4 for mixed crystallization, and finally the solid monoammonium phosphate is obtained by carrying out fixed separation treatment through the centrifuge 10.
As described above, in the practical implementation, the separation liquid output by the centrifuge 10 is returned to the crystallization kettle 4 through a pipeline, so as to be recycled.
As described above, in the implementation, the controlled conveying device 9 is a controlled power pump or a controlled valve, so as to control the conveying of the third mixed solution in the storage container 8 to the crystallization kettle 4.
As described above, in practice, the concentration device 3 may employ an MVR system.
As described above, the scheme protects a treatment method of a waste phosphoric acid flowing water treatment line, and all technical schemes which are the same as or similar to the scheme are shown to fall into the protection scope of the scheme.
Claims (6)
1. The method for treating the waste phosphoric acid by using the flow line is characterized by comprising a first reaction kettle (1) for allowing a part of waste phosphoric acid and ammonia water to react therein to obtain a first solid-liquid mixture, a first filter press (2) for performing solid-liquid separation treatment on the first solid-liquid mixture output by the first reaction kettle (1) to obtain a first mixed liquid and first filter residues, a concentrating device (3) for concentrating the first mixed liquid output by the first filter press (2) to obtain a first concentrated liquid, a crystallization kettle (4) for storing the first concentrated liquid output by the concentrating device (3), a second reaction kettle (5) for allowing a part of waste phosphoric acid and ammonia water to react therein to obtain a second solid-liquid mixture, a second filter press (6) for performing solid-liquid separation treatment on the second solid-liquid mixture output by the second reaction kettle (5) to obtain a second mixed liquid and second filter residues, a concentrating device (3) for concentrating the first mixed liquid output by an ion exchange resin to obtain a third mixed liquid, a crystallization kettle (8) for controlling the crystallization kettle (4) to be delivered to a controlled system (10), and a third centrifuge (8) for delivering the mixed liquid to the storage kettle (4);
the processing method comprises the following steps:
step A, taking a part of waste phosphoric acid, adding ammonia water into the waste phosphoric acid, regulating the pH value to be in a range of 5.3-5.5 to obtain a first solid-liquid mixture, then carrying out solid-liquid separation treatment on the first solid-liquid mixture to obtain a first mixed solution containing diammonium phosphate and a first filter residue containing aluminum hydroxide and aluminum hydrogen phosphate, and then concentrating the first mixed solution to obtain a first concentrated solution;
step B, taking a part of waste phosphoric acid, adding ammonia water into the waste phosphoric acid, regulating the pH value to be in a range of 4.1-4.3 to obtain a second solid-liquid mixture, then carrying out solid-liquid separation treatment on the second solid-liquid mixture to obtain a second mixed solution containing phosphoric acid, monoammonium phosphate and aluminum ions and a second filter residue containing aluminum dihydrogen phosphate, then allowing the second mixed solution to enter an ion exchange system, and adsorbing the aluminum ions in the second mixed solution by using aluminum ion exchange resin to obtain a third mixed solution containing monoammonium phosphate and phosphoric acid;
step C, gradually adding the third mixed solution obtained in the step B into the first concentrated solution obtained in the step A, adjusting the pH value to be in a range of 4.3-4.5, crystallizing, and then carrying out solid-liquid separation treatment to obtain monoammonium phosphate solid and separating liquid;
and (3) when the waste phosphoric acid is taken in the step A and the step B, carrying out the step A treatment on the waste phosphoric acid with the phosphoric acid content of less than 30%, and carrying out the step B treatment on the waste phosphoric acid with the phosphoric acid content of not less than 30%.
2. The method for treating waste phosphoric acid in a line according to claim 1, wherein the concentration of ammonia water used in the step A and the step B is 25% or more.
3. The method for treating waste phosphoric acid in a line according to claim 1, wherein in the step a, the concentration of the first mixed solution is controlled so that the effective phosphorus content of the concentrated solution is in the range of 250 to 300 g/l.
4. The method for treating waste phosphoric acid in a line according to claim 1, further comprising a step D of returning the separated liquid obtained after the solid-liquid separation in the step C to the crystallization process for reuse.
5. The method according to claim 1, wherein the first residue obtained in the step A and the second residue obtained in the step B are treated as industrial solid waste.
6. The method for treating waste phosphoric acid in a line according to any one of claims 1 to 5, wherein the separated liquid from the centrifuge (10) is returned to the crystallization vessel (4) through a pipe.
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