CN109250856A - It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource - Google Patents

It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource Download PDF

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CN109250856A
CN109250856A CN201811218572.1A CN201811218572A CN109250856A CN 109250856 A CN109250856 A CN 109250856A CN 201811218572 A CN201811218572 A CN 201811218572A CN 109250856 A CN109250856 A CN 109250856A
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mixed liquor
ferric phosphate
resource
containing wastewater
recovery method
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李智军
孙资光
丁建华
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Hunan City Ya New Materials Co Ltd
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Hunan City Ya New Materials Co Ltd
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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
    • 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
    • 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
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • 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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • 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
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • 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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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
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Abstract

The invention discloses a kind of inexpensive ferric phosphate nitrogen-containing wastewater processing and recovery method as resource.Described method includes following steps: step S1, and ammonium hydroxide is added into ferric phosphate mother liquor, and pH value is adjusted to 6-6.8, and the first mixed liquor is obtained by filtration；Wherein the first mixed liquor mainly includes ingredient (NH4)2SO4And NH4H2PO4；First mixed liquor is carried out film concentration, obtains the second mixed liquor by step S2；Second mixed liquor is carried out MVR evaporation, isolated ammonia sulfate crystal and ammonium dihydrogen phosphate crystal by step S3；Step S4, crystal washing, drying, respectively obtains ammonium sulfate and biphosphate ammonium product.Low cost ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, simple process, the cost of raw materials used ammonium hydroxide are low, compared to the prior art, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource have more preferably economic value.

Description

It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource
Technical field
The present invention relates to industrial waste water treatment, in particular to a kind of inexpensive ferric phosphate nitrogen-containing wastewater processing And recovery method as resource.
Background technique
With the development of the times with the progress of science and technology, the mankind are increasing for the demand of new energy materials.Wherein, lithium electricity Pond is widely used to all kinds of mobile communication because of the advantages that its voltage is high, energy density is big, good cycle, hot properties are good In equipment, the vehicles.The positive electrode of lithium battery mainly uses ferric phosphate.The preparation process of traditional ferric phosphate mainly includes Coprecipitation, hydro-thermal method etc., wherein coprecipitation using relatively broad.
Coprecipitation, which will refer to, other compounds will be added to be made to be precipitated and precipitate, carry out later after source of iron and phosphorus source dissolution Washing, dry, calcining obtain ferric phosphate product.During traditional co-precipitation method prepares ferric phosphate, a large amount of nitrogenous, phosphorus are generated Waste mother liquor.In existing production technology, cannot not only recycle the useful component of ferric phosphate mother liquor, and need using it is complicated, Expensive technique is effectively treated the pollutants such as nitrogen, phosphoric acid in mother liquor, causes the serious wasting of resources and enterprise raw Produce the increase of cost, environmental protection pressure.
For the technical problem, and the prior art (Chinese Patent Application No.: 201710856857.7, a kind of patent name " phosphorus The circulation utilization method of mother liquor in sour iron production process ") disclose a kind of nitrogen by mother liquor, the side that reclamation of phosphorus resource utilizes Method, technical solution include: by FeSO4、H2O2And H2SO4Mixing carries out oxidation reaction, obtains ferric sulfate material liquid；By ferric sulfate original Feed liquid is reacted with the mixing of ferric phosphate mother liquor, ferric phosphate is obtained, to recycle the phosphorus in mother liquor；During preparing ferric phosphate Lime white is added in filtrate, and stripping processing is carried out to mixed filtrate, the ammonia that stripping generates is absorbed using phosphoric acid, obtained NH4H2PO4Solution realizes the nitrogen in recycling mother liquor.
Above-mentioned technical proposal, the product NH that recycling nitrogen technique is prepared4H2PO4As the phosphorus in ferric phosphate production process Source, the market price lead to the at high cost of nitrogen recovery process far below raw material phosphoric acid used in nitrogen recovery process, the technique The disadvantages of economic value is not high.
It is asked in consideration of it, solving above-mentioned technology it is necessary to provide a kind of ferric phosphate nitrogen-containing wastewater processing method at low cost Topic.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of inexpensive ferric phosphate nitrogen-containing wastewater processing and resource reclaims Method, at low cost, economic value is high.
To solve the above-mentioned problems, technical scheme is as follows:
It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource, include the following steps:
Step S1, is added ammonium hydroxide into ferric phosphate mother liquor, and pH value is adjusted to 6-6.8, and the first mixed liquor is obtained by filtration；Wherein First mixed liquor mainly includes ingredient (NH4)2SO4And NH4H2PO4；
First mixed liquor is carried out the first film concentration, obtains the second mixed liquor by step S2；
Second mixed liquor is carried out MVR evaporation, isolated ammonia sulfate crystal and ammonium dihydrogen phosphate crystal by step S3；
Step S4, crystal washing, drying, respectively obtains ammonium sulfate and biphosphate ammonium product.
Further, in step S1, the mass concentration of ammonium hydroxide used is 15%-25%.
Further, in step S1, the mass concentration of the first mixed liquor is 6-8%.
It further, further include that the first mixed liquor is subjected to ion exchange resin removal step before step S2, with removal Fe in first mixed liquor.
Further, in step S2, the mass concentration of the second mixed liquor is 12-15%.
Further, step S3 is specifically included:
Second mixed liquor is carried out MVR evaporation, obtains magma by step S31；
Magma is centrifuged to obtain pure ammonia sulfate crystal by step S32；
The mother liquor of 80-90% after centrifugation is returned to MVR evaporator and continues to be concentrated by evaporation by step S33, another 10-20% Mother liquor carry out decrease temperature crystalline, obtain ammonium dihydrogen phosphate crystal.
Further, in step S3, the crystallization temperature for controlling ammonium dihydrogen phosphate crystal is 30-50 DEG C.
Further, in step S4, cold water washing ammonia sulfate crystal and ammonium dihydrogen phosphate crystal is respectively adopted.
Further, in step S4, the temperature of washing water used is 5-20 DEG C, and washing water is the 10- of crystal weight 30%.
Further, further includes: generate MVR evaporation in the permeate of the first film of step S2 concentration generation, step S3 Condensed water carries out the reverse osmosis purified treatment of pure water, and the washing water for washing ferric phosphate filter cake is carried out processing step；
Wherein, the washing water for washing ferric phosphate filter cake is handled, is included the following steps:
Ammonium hydroxide is added into washing water, pH value is adjusted to 6-6.8, third mixed liquor is obtained by filtration；
Third mixed liquor is subjected to the second film concentration, obtained concentrate is mixed with the first mixed liquor, and permeate carries out pure The reverse osmosis purified treatment of water.
Compared with prior art, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, Beneficial effect is:
One, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, by into mother liquor Ammonium hydroxide is added, adjusts pH value to 6-6.8, makes the ingredient in solution with (NH4)2SO4、NH4H2PO4Based on；Then it will be obtained by filtration Solution successively carries out film concentration, MVR evaporation process, isolated (NH4)2SO4、NH4H2PO4Two kinds of crystal realize that ferric phosphate is female The recycling of nitrogen, phosphorus in liquid.The processing method simple process, the cost of raw materials used ammonium hydroxide are low, therefore, compared to existing skill Art, low cost ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource have more preferably economic value.
Two, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, are evaporated using MVR and are tied The salinity substance in waste water is converted crystal by brilliant method, then divides salt and cold water to wash skill using freezing crystal salt-mixture Art carries out separating-purifying, and by crystallization temperature in control purification technique, temperature of washing water, washing water consumption etc. because Element obtains the higher ammonium phosphate of purity and ammonium dihydrogen phosphate.Through detecting, the two purity reachable 95% or more, economic value Higher than the economic value of salt-mixture, application is unrestricted.
Three, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, ferric phosphate produce work The nitrogen in waste water, the phosphor resource generated in skill is fully utilized, and wastewater treatment is made to realize zero-emission.
Four, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, are evaporated using MVR and are tied Crystalline substance processing waste water, makes the salinity Crystallization Separation in waste water, cost for wastewater treatment is low.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other Attached drawing.
Fig. 1 is inexpensive ferric phosphate nitrogen-containing wastewater processing and the process signal of recovery method as resource provided by the invention Figure.
Specific embodiment
Technical solution in embodiment in order to enable those skilled in the art to better understand the present invention, and make of the invention Above objects, features, and advantages can be more obvious and easy to understand, with reference to the accompanying drawing makees a specific embodiment of the invention into one The explanation of step.
It should be noted that being used to help understand the present invention for the explanation of these embodiments, but do not constitute Limitation of the invention.In addition, as long as technical characteristic involved in the various embodiments of the present invention described below is each other Between do not constitute conflict and can be combined with each other.
The preparation process of ferric phosphate is as follows:
By ferric phosphate reaction raw materials liquid (NH4H2PO4、FeSO4、H3PO4Mixed liquor) and H2O2Redox occurs for mixing anti- It answers, reaction equation is as follows:
2NH4H2PO4+2FeSO4+H2O2=2FePO4↓+2NH4HSO4+2H2O
H in reaction raw materials3PO4Reaction is not participated in directly, and main function is the acidity adjusted in reaction process.
Reacting slurry filters pressing is obtained into ferric phosphate filter cake and ferric phosphate mother liquor, ferric phosphate filter cake passes through the works such as washing, calcining Sequence obtains phosphoric acid iron product；The pH value of ferric phosphate mother liquor is 1-2.5, mainly includes ingredient NH4HSO4、H3PO4, i.e. ferric phosphate is female It mainly include NH in liquid4 +、H+、SO4 2-、PO4 3-, in addition to this, also containing impurity such as a small amount of Fe.
The pH value of ferric phosphate Washing of Filter Cake water is 2-3, contains a small amount of SO4 2-、PO4 3-And Fe impurity.
It is an object of the invention to the waste water that phosphoric acid process for making iron is generated (comprising ferric phosphate mother liquor and washing water) into Row processing, and wastewater treatment method through the invention make the nitrogen in waste water, phosphorus realize resource recycling, reach waste water Zero-emission.
Below by way of specific embodiment to inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and resource Recovery method is described in detail.
Embodiment 1
Referring to Fig. 1, being the stream of inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource Journey schematic diagram.It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource, include the following steps:
The ammonium hydroxide that mass concentration is 20% is added into ferric phosphate mother liquor, pH value is adjusted to 6.5, is obtained by filtration by step S1 First mixed liquor；Reaction equation is as follows:
H++OH-=H2O (1)
NH3+H3PO4=NH4H2PO4 (2)
Fe3++3OH-=Fe (OH)3↓ (3)
The impurity such as the iron hydroxide in filtering removal mother liquor, making the first mixed liquor mainly includes ingredient (NH4)2SO4With NH4H2PO4；In this implementation, the mass concentration of the first solution is 7%.
Preferably, filtered first mixed liquor is subjected to ion exchange resin removal of impurities in resin adsorption tower, further The iron ion in the first mixed solution is removed, Fe ion concentration in the first mixed solution is made to be lower than 3-5ppm.
First mixed liquor is carried out the first film concentration by step S2, obtains the second mixed liquor that mass concentration is 13.5%；
The concentration of first film uses super-pressure reverse osmosis membrane processing technique, and it is anti-that the permeate that the concentration of the first film generates carries out pure water Purified treatment is permeated, the second mixed liquor is that concentrate enters step S3；
Second mixed liquor is carried out MVR evaporation, isolated ammonia sulfate crystal and ammonium dihydrogen phosphate crystal by step S3；
Specifically, using freezing separation technology after evaporative crystallization, comprising:
Second mixed liquor is carried out MVR evaporation, obtains magma by step S31；
Magma is centrifuged to obtain pure ammonia sulfate crystal by step S32；
After centrifugation 80% mother liquor is returned to MVR evaporator and continues to be concentrated by evaporation by step S33, another 20% mother liquor Decrease temperature crystalline is carried out, control crystallization temperature is 30 DEG C, obtains ammonium dihydrogen phosphate crystal.
It should be noted that calculate by volume herein.
Step S4, crystal washing, drying, respectively obtains ammonium sulfate and biphosphate ammonium product；
In the present embodiment, cold water washing ammonia sulfate crystal and ammonium dihydrogen phosphate crystal is respectively adopted, obtains ammonium phosphate and phosphorus Acid dihydride ammonium product enables the nitrogen in ferric phosphate mother liquor, phosphorus to return in a manner of two kinds of ammonium sulfate, ammonium dihydrogen phosphate products respectively It receives, ammonium dihydrogen phosphate is as ferric phosphate reaction raw materials application.
Crystal wash conditions are as follows:
The water temperature of washing water used is 5-20 DEG C, and washing water is the 10% of crystal weight.Obtained ammonium sulfate and phosphoric acid The purity of ammonium dihydrogen is 95% or more.
In crystal washing process, in addition to upper embodiment, it can also be washed using corresponding saturated solution.
In the present embodiment, in order to further increase water treatment effect, by the first film of step S2 concentration generate permeate, The condensed water progress reverse osmosis purified treatment of pure water that MVR evaporation generates in step S3, the purified water qualified discharge of reverse osmosis treatment, Concentrate recycling purifies again.
In order to further satisfaction phosphoric acid process for making iron generate discharged wastewater met the national standard, it is preferred that the washing water of generation into The following processing step of row:
It is 20% ammonium hydroxide that mass concentration is added into washing water, and pH value is adjusted to 6.5, third mixed liquor is obtained by filtration；
Third mixed liquor is subjected to the second film concentration, obtained concentrate is mixed with the first mixed liquor, and permeate carries out pure The reverse osmosis purified treatment of water.Wherein the second film concentration uses reverse osmosis membrane concentration technology.
By the waste water that the processing method of the present embodiment is handled, TDS content is less than 2.5mg/L, conductivity≤10us/ cm.Nitrogen, phosphorus in waste water are sufficiently recycled, and realize wastewater zero discharge.
Wastewater treatment and resource reclaim based on embodiment 1 are theoretical, wastewater treatment and the resource reclaim reason of following embodiment By same as Example 1, difference is to change the parameter of each processing step.
Embodiment 2
It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource, include the following steps:
The ammonium hydroxide that mass concentration is 15% is added into ferric phosphate mother liquor, pH value is adjusted to 6, is obtained by filtration the by step S1 One mixed liquor；Wherein the first mixed liquor mainly includes ingredient (NH4)2SO4And NH4H2PO4, mass concentration 6%；
Filtered first mixed liquor carries out ion exchange resin removal of impurities in resin adsorption tower, and further removal first is mixed The iron ion in solution is closed, Fe ion concentration in the first mixed solution is made to be lower than 3-5ppm.
First mixed liquor is carried out the first film concentration by step S2, obtains the second mixed liquor that mass concentration is 12%；
Second mixed liquor is carried out MVR evaporation, isolated ammonia sulfate crystal and ammonium dihydrogen phosphate crystal by step S3；
Specifically, using freezing separation technology after evaporative crystallization, comprising:
Second mixed liquor is carried out MVR evaporation, obtains magma by step S31；
Magma is centrifuged to obtain pure ammonia sulfate crystal by step S32；
After centrifugation 90% mother liquor is returned to MVR evaporator and continues to be concentrated by evaporation by step S33, another 10% mother liquor Decrease temperature crystalline is carried out, control crystallization temperature is 40 DEG C, obtains ammonium dihydrogen phosphate crystal.
Step S4, crystal washing, drying, respectively obtains ammonium sulfate and biphosphate ammonium product；
Crystal wash conditions are as follows:
The water temperature of washing water used is 15 DEG C, and washing water is the 20% of crystal weight.Obtained ammonium sulfate and di(2-ethylhexyl)phosphate The purity of hydrogen ammonium is 95% or more.
In the present embodiment, by the condensed water that MVR evaporation generates in the permeate of the first film of step S2 concentration generation, step S3 Carry out the reverse osmosis purified treatment of pure water.
Step is handled as follows in the washing water that phosphoric acid process for making iron generates:
It is 15% ammonium hydroxide that mass concentration is added into washing water, and pH value is adjusted to 6, third mixed liquor is obtained by filtration；
Third mixed liquor is subjected to the second film concentration, obtained concentrate is mixed with the first mixed liquor, and permeate carries out pure The reverse osmosis purified treatment of water.
By the waste water that the processing method of the present embodiment is handled, TDS content is less than 2.8mg/L, conductivity≤10us/ cm.Nitrogen, phosphorus in waste water are sufficiently recycled, and realize wastewater zero discharge.
Embodiment 3
It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource, include the following steps:
The ammonium hydroxide that mass concentration is 22% is added into ferric phosphate mother liquor, pH value is adjusted to 6.8, is obtained by filtration by step S1 First mixed liquor；Wherein the first mixed liquor mainly includes ingredient (NH4)2SO4And NH4H2PO4, mass concentration 8%；
Filtered first mixed liquor carries out ion exchange resin removal of impurities in resin adsorption tower, and further removal first is mixed The iron ion in solution is closed, Fe ion concentration in the first mixed solution is made to be lower than 3-5ppm.
First mixed liquor is carried out the first film concentration by step S2, obtains the second mixed liquor that mass concentration is 14%；
Second mixed liquor is carried out MVR evaporation, isolated ammonia sulfate crystal and ammonium dihydrogen phosphate crystal by step S3；
Specifically, using freezing separation technology after evaporative crystallization, comprising:
Second mixed liquor is carried out MVR evaporation, obtains magma by step S31；
Magma is centrifuged to obtain pure ammonia sulfate crystal by step S32；
After centrifugation 85% mother liquor is returned to MVR evaporator and continues to be concentrated by evaporation by step S33, another 15% mother liquor Decrease temperature crystalline is carried out, control crystallization temperature is 50 DEG C, obtains ammonium dihydrogen phosphate crystal.
Step S4, crystal washing, drying, respectively obtains ammonium sulfate and biphosphate ammonium product；
Crystal wash conditions are as follows:
The water temperature of washing water used is 5 DEG C, and washing water is the 30% of crystal weight.Obtained ammonium sulfate and biphosphate The purity of ammonium is 95% or more.
In the present embodiment, by the condensed water that MVR evaporation generates in the permeate of the first film of step S2 concentration generation, step S3 Carry out the reverse osmosis purified treatment of pure water.
Step is handled as follows in the washing water that phosphoric acid process for making iron generates:
It is 22% ammonium hydroxide that mass concentration is added into washing water, and pH value is adjusted to 6.8, third mixed liquor is obtained by filtration；
Third mixed liquor is subjected to the second film concentration, obtained concentrate is mixed with the first mixed liquor, and permeate carries out pure The reverse osmosis purified treatment of water.
By the waste water that the processing method of the present embodiment is handled, TDS content is less than 2.6mg/L, conductivity≤10us/ cm.Nitrogen, phosphorus in waste water are sufficiently recycled, and realize wastewater zero discharge.
Embodiment 4
It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource, include the following steps:
The ammonium hydroxide that mass concentration is 25% is added into ferric phosphate mother liquor, pH value is adjusted to 6.7, is obtained by filtration by step S1 First mixed liquor；Wherein the first mixed liquor mainly includes ingredient (NH4)2SO4And NH4H2PO4, mass concentration 7%；
Filtered first mixed liquor carries out ion exchange resin removal of impurities in resin adsorption tower, and further removal first is mixed The iron ion in solution is closed, Fe ion concentration in the first mixed solution is made to be lower than 3-5ppm.
First mixed liquor is carried out the first film concentration by step S2, obtains the second mixed liquor that mass concentration is 15%；
Second mixed liquor is carried out MVR evaporation, isolated ammonia sulfate crystal and ammonium dihydrogen phosphate crystal by step S3；
Specifically, using freezing separation technology after evaporative crystallization, comprising:
Second mixed liquor is carried out MVR evaporation, obtains magma by step S31；
Magma is centrifuged to obtain pure ammonia sulfate crystal by step S32；
After centrifugation 87% mother liquor is returned to MVR evaporator and continues to be concentrated by evaporation by step S33, another 13% mother liquor Decrease temperature crystalline is carried out, control crystallization temperature is 35 DEG C, obtains ammonium dihydrogen phosphate crystal.
Step S4, crystal washing, drying, respectively obtains ammonium sulfate and biphosphate ammonium product；
Crystal wash conditions are as follows:
The water temperature of washing water used is 20 DEG C, and washing water is the 30% of crystal weight.Obtained ammonium sulfate and di(2-ethylhexyl)phosphate The purity of hydrogen ammonium is 95% or more.
In the present embodiment, by the condensed water that MVR evaporation generates in the permeate of the first film of step S2 concentration generation, step S3 Carry out the reverse osmosis purified treatment of pure water.
Step is handled as follows in the washing water that phosphoric acid process for making iron generates:
It is 25% ammonium hydroxide that mass concentration is added into washing water, and pH value is adjusted to 6.7, third mixed liquor is obtained by filtration；
Third mixed liquor is subjected to the second film concentration, obtained concentrate is mixed with the first mixed liquor, and permeate carries out pure The reverse osmosis purified treatment of water.
By the waste water that the processing method of the present embodiment is handled, TDS content is less than 2.7mg/L, conductivity≤10us/ cm.Nitrogen, phosphorus in waste water are sufficiently recycled, and realize wastewater zero discharge.
In the present invention, freezing separation and cold water washing technology are carried out using MVR evaporative crystallization, and by crystallized mixed salt, is obtained To the ammonium sulfate and ammonium dihydrogen phosphate product of higher degree.It wherein separates and the parameter of washing process to the purity of product and is returned Yield has larger impact.It is described in detail below by way of comparative example.
The influence of 1 mother liquor decrease temperature crystalline amount of comparative example
On the basis of embodiment 1, by step S33, the amount that centrifugation post mother liquor carries out decrease temperature crystalline is designed as 30%, returns It returns the amount that MVR evaporator continues to be concentrated by evaporation and is designed as 70%, other process conditions are constant.
The washed drying of obtained crystal measures the purity of ammonium sulfate up to 95%, and the purity of ammonium dihydrogen phosphate is 90%.
The influence of 2 crystallization temperature of comparative example
On the basis of embodiment 1, by step S33, the crystallization temperature control of ammonium dihydrogen phosphate is at 60 DEG C, other techniques Condition is constant.
The washed drying of obtained crystal, obtained ammonium sulfate purity is 95% or more, and ammonium dihydrogen phosphate purity is 92%.
The influence of the washing water of comparative example 3
It on that basis of example 1, is the 40% of crystal total amount by washing water in step S4 and controlling.Under this condition, though The salinity purity is high so obtained causes partial crystals to dissolve, so that ammonium sulfate up to 95 or more, but since washing water consumption is excessive It is reduced with the rate of recovery of ammonium dihydrogen phosphate.
If by wash water control for crystal total amount 10% hereinafter, if will affect crystal washing effect, make ammonium sulfate and The purity of ammonium dihydrogen phosphate reduces.
The influence of 4 temperature of washing water of comparative example
On that basis of example 1, temperature of washing water in step S4 is designed as 25 DEG C.Other process conditions are constant.
At the process conditions, the rate of recovery of ammonium sulfate and ammonium dihydrogen phosphate is equally influenced.
From this analysis, cooling mother liquor amount, ammonium dihydrogen phosphate crystallization temperature, washing water consumption and temperature are to isolated Ammonium sulfate and purity, the rate of recovery of ammonium dihydrogen phosphate have large effect.
Compared with prior art, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, Beneficial effect is:
One, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, by into mother liquor Ammonium hydroxide is added, adjusts pH value to 6-6.8, makes the ingredient in solution with (NH4)2SO4、NH4H2PO4Based on；Then it will be obtained by filtration Solution successively carries out film concentration, MVR evaporation process, separates (NH4)2SO4、NH4H2PO4Two kinds of crystal are realized in ferric phosphate mother liquor The recycling of nitrogen, phosphorus.The processing method simple process, the cost of raw materials used ammonium hydroxide are low, therefore, compared to the prior art, Low cost ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource have more preferably economic value.
Two, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, are evaporated using MVR and are tied The salinity substance in waste water is converted crystal by brilliant method, then divides salt and cold water to wash skill using freezing crystal salt-mixture Art carries out separating-purifying, and by crystallization temperature in control purification technique, temperature of washing water, washing water consumption etc. because Element obtains the higher ammonium phosphate of purity and ammonium dihydrogen phosphate.Through detecting, the two purity reachable 95% or more, economic value Higher than the economic value of salt-mixture, application is unrestricted.
Three, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, ferric phosphate produce work The nitrogen in waste water, the phosphor resource generated in skill is fully utilized, and wastewater treatment is made to realize zero-emission.
Four, inexpensive ferric phosphate nitrogen-containing wastewater processing provided by the invention and recovery method as resource, are evaporated using MVR and are tied Crystalline substance processing waste water, makes the salinity Crystallization Separation in waste water, cost for wastewater treatment is low.
It is embodiments of the present invention to be explained in detail, but the present invention is not limited to described embodiment party above Formula.To those skilled in the art, these embodiments are carried out without departing from the principles and spirit of the present invention A variety of change, modification, replacement and modification still fall within protection scope of the present invention.

Claims (10)

1. a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource, which comprises the steps of:
Step S1, is added ammonium hydroxide into ferric phosphate mother liquor, and pH value is adjusted to 6-6.8, and the first mixed liquor is obtained by filtration；Wherein first Mixed liquor mainly includes ingredient (NH4)2SO4And NH4H2PO4；
First mixed liquor is carried out the first film concentration, obtains the second mixed liquor by step S2；
Second mixed liquor is carried out MVR evaporation, isolated ammonia sulfate crystal and ammonium dihydrogen phosphate crystal by step S3；
Step S4, crystal washing, drying, respectively obtains ammonium sulfate and biphosphate ammonium product.
2. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 1 and recovery method as resource, which is characterized in that In step S1, the mass concentration of ammonium hydroxide used is 15%-25%.
3. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 1 and recovery method as resource, which is characterized in that In step S1, the mass concentration of the first mixed liquor is 6-8%.
4. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 1 and recovery method as resource, which is characterized in that It further include that the first mixed liquor is subjected to ion exchange resin removal step before step S2.
5. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 1 and recovery method as resource, which is characterized in that In step S2, the mass concentration of the second mixed liquor is 12-15%.
6. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 1 and recovery method as resource, which is characterized in that Step S3 is specifically included:
Second mixed liquor is carried out MVR evaporation, obtains magma by step S31；
Magma is centrifuged to obtain pure ammonia sulfate crystal by step S32；
The mother liquor of 80-90% after centrifugation is returned to MVR evaporator and continues to be concentrated by evaporation by step S33, the mother of another 10-20% Liquid carries out decrease temperature crystalline, obtains ammonium dihydrogen phosphate crystal.
7. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 6 and recovery method as resource, which is characterized in that In step S3, the crystallization temperature for controlling ammonium dihydrogen phosphate crystal is 30-50 DEG C.
8. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 1 and recovery method as resource, which is characterized in that In step S4, cold water washing ammonia sulfate crystal and ammonium dihydrogen phosphate crystal is respectively adopted.
9. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 8 and recovery method as resource, which is characterized in that In step S4, the temperature of washing water used is 5-20 DEG C, and washing water is the 10-30% of crystal weight.
10. low cost ferric phosphate nitrogen-containing wastewater processing according to claim 1 to 9 and recovery method as resource, It is characterized by further comprising: by the condensed water that MVR evaporation generates in the permeate of the first film of step S2 concentration generation, step S3 The reverse osmosis purified treatment of pure water is carried out, and the washing water for washing ferric phosphate filter cake is subjected to processing step；
Wherein, the washing water for washing ferric phosphate filter cake is handled, is included the following steps:
Ammonium hydroxide is added into washing water, pH value is adjusted to 6-6.8, third mixed liquor is obtained by filtration；
Third mixed liquor is subjected to the second film concentration, obtained concentrate is mixed with the first mixed liquor, and it is anti-that permeate carries out pure water Permeate purified treatment.
CN201811218572.1A 2018-10-19 2018-10-19 It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource Pending CN109250856A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109734237A (en) * 2019-03-06 2019-05-10 深圳海纳百川科技有限公司 A kind of ferric phosphate production wastewater treatment process and processing equipment
CN110002415A (en) * 2019-04-01 2019-07-12 湖南中金岭南康盟环保科技有限公司 A method of phosphate radical and sulfate radical are recycled from ferric phosphate production waste water
CN110540185A (en) * 2019-09-17 2019-12-06 襄阳泽东新能源发展有限公司 synthesis process of battery-grade iron phosphate
CN110589788A (en) * 2019-09-17 2019-12-20 襄阳泽东新能源发展有限公司 Method for recycling wastewater in battery-grade iron phosphate synthesis process
CN113307243A (en) * 2021-07-08 2021-08-27 河南佰利新能源材料有限公司 Method for preparing iron phosphate by recycling mother liquor
CN113354177A (en) * 2021-07-06 2021-09-07 杭州逐真科技有限公司 System and method for full-element resource treatment of iron phosphate ammonia nitrogen-containing wastewater
CN114195316A (en) * 2021-12-31 2022-03-18 中化(浙江)膜产业发展有限公司 Iron phosphate wastewater treatment system and treatment method
CN115057455A (en) * 2022-07-20 2022-09-16 瓮福（集团）有限责任公司 Process and device for producing granular ammonium sulfate by purifying iron phosphate mother liquor
CN115124178A (en) * 2022-07-21 2022-09-30 江苏卓博环保科技有限公司 Recycling treatment device and method for wastewater generated in iron phosphate production by ammonia process
CN115231758A (en) * 2022-08-18 2022-10-25 雅安天蓝新材料科技有限公司 Treatment method of iron phosphate wastewater and method for preparing fertilizer by using iron phosphate wastewater
CN115340240A (en) * 2022-08-24 2022-11-15 广东邦普循环科技有限公司 Comprehensive treatment method of wastewater
CN115818599A (en) * 2022-12-29 2023-03-21 四川安宁铁钛股份有限公司 Method for recycling wastewater generated in iron phosphate production
CN116903182A (en) * 2023-08-03 2023-10-20 湖北朗润环保科技有限公司 Method and system for treating iron phosphate wastewater
CN117447007A (en) * 2023-10-26 2024-01-26 湖北美辰环保股份有限公司 Process for separating ammonium sulfate and ammonium phosphate from iron phosphate production wastewater

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104609631A (en) * 2015-01-19 2015-05-13 山东国信环境系统股份有限公司 High-salt iron phosphate liquid waste zero-emission treatment device and method
CN105000744A (en) * 2015-08-18 2015-10-28 深圳市华虹清源环保科技有限公司 Iron phosphate wastewater treatment and recycling device and method
CN107082522A (en) * 2017-05-10 2017-08-22 绍兴齐英膜科技有限公司 A kind of handling process and processing unit of phosphoric acid iron waste water
CN107619056A (en) * 2017-09-19 2018-01-23 江西赣锋锂业股份有限公司 A kind of ferric phosphate disposing mother liquor utilizes the method for preparing ammonium chloride

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104609631A (en) * 2015-01-19 2015-05-13 山东国信环境系统股份有限公司 High-salt iron phosphate liquid waste zero-emission treatment device and method
CN105000744A (en) * 2015-08-18 2015-10-28 深圳市华虹清源环保科技有限公司 Iron phosphate wastewater treatment and recycling device and method
CN107082522A (en) * 2017-05-10 2017-08-22 绍兴齐英膜科技有限公司 A kind of handling process and processing unit of phosphoric acid iron waste water
CN107619056A (en) * 2017-09-19 2018-01-23 江西赣锋锂业股份有限公司 A kind of ferric phosphate disposing mother liquor utilizes the method for preparing ammonium chloride

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘丙伟主编: "《初中化学基础知识手册》", 30 April 2014 *
化学工业部建设协调司、化工部硫酸和磷肥设计技术中心主编: "《磷酸 磷铵 重钙技术与设计手册》", 31 January 1997 *
叶铁林主编: "《化工结晶过程原理及应用》", 30 April 2006 *

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CN109734237A (en) * 2019-03-06 2019-05-10 深圳海纳百川科技有限公司 A kind of ferric phosphate production wastewater treatment process and processing equipment
CN110002415A (en) * 2019-04-01 2019-07-12 湖南中金岭南康盟环保科技有限公司 A method of phosphate radical and sulfate radical are recycled from ferric phosphate production waste water
CN110540185A (en) * 2019-09-17 2019-12-06 襄阳泽东新能源发展有限公司 synthesis process of battery-grade iron phosphate
CN110589788A (en) * 2019-09-17 2019-12-20 襄阳泽东新能源发展有限公司 Method for recycling wastewater in battery-grade iron phosphate synthesis process
CN113354177B (en) * 2021-07-06 2023-05-30 杭州逐真科技有限公司 System and method for recycling iron phosphate ammonia nitrogen-containing wastewater
CN113354177A (en) * 2021-07-06 2021-09-07 杭州逐真科技有限公司 System and method for full-element resource treatment of iron phosphate ammonia nitrogen-containing wastewater
CN113307243A (en) * 2021-07-08 2021-08-27 河南佰利新能源材料有限公司 Method for preparing iron phosphate by recycling mother liquor
CN114195316A (en) * 2021-12-31 2022-03-18 中化(浙江)膜产业发展有限公司 Iron phosphate wastewater treatment system and treatment method
CN114195316B (en) * 2021-12-31 2024-07-12 中膜(浙江)环保科技有限公司 Ferric phosphate wastewater treatment system and treatment method
CN115057455A (en) * 2022-07-20 2022-09-16 瓮福（集团）有限责任公司 Process and device for producing granular ammonium sulfate by purifying iron phosphate mother liquor
CN115124178A (en) * 2022-07-21 2022-09-30 江苏卓博环保科技有限公司 Recycling treatment device and method for wastewater generated in iron phosphate production by ammonia process
CN115124178B (en) * 2022-07-21 2024-06-11 江苏卓博环保科技有限公司 Recycling treatment device and method for wastewater from ammonia ferric phosphate production
CN115231758A (en) * 2022-08-18 2022-10-25 雅安天蓝新材料科技有限公司 Treatment method of iron phosphate wastewater and method for preparing fertilizer by using iron phosphate wastewater
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Application publication date: 20190122