CN110002415A - A method of phosphate radical and sulfate radical are recycled from ferric phosphate production waste water - Google Patents
A method of phosphate radical and sulfate radical are recycled from ferric phosphate production waste water Download PDFInfo
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- CN110002415A CN110002415A CN201910258681.4A CN201910258681A CN110002415A CN 110002415 A CN110002415 A CN 110002415A CN 201910258681 A CN201910258681 A CN 201910258681A CN 110002415 A CN110002415 A CN 110002415A
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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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
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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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention provides it is a kind of from ferric phosphate production waste water in recycle phosphate radical and sulfate radical method, specifically: (1) into ferric phosphate mother liquor be added Ca (OH)2It is reacted, obtains the first precipitation slag and the first precipitated liquid；(2) it is added into the first precipitated liquid and is reacted containing ammonia solution, obtain the second precipitation slag and the second precipitated liquid；(3) phosphogypsum is obtained after mixing the first precipitation slag and the second precipitation slag, is added into ferric phosphate mother liquor, reaction obtains conversion filtrate and calcium sulfate；(4) conversion filtrate is back in step (1), stops adding ferric phosphate mother liquor, repeats step (1), (2) and (3)；(5) the second precipitated liquid and acid solution are mixed to get neutralization and adjust liquid, carried out reverse osmosis, evaporation, crystallization to adjusting liquid is neutralized, obtain ammonium sulfate solids and monoammonium phosphate solid.This method can realize being kept completely separate and thoroughly recycling for Phosphorus From Wastewater acid group and sulfate radical, and phosphate radical product and sulfate radical product purity are higher.
Description
Technical field
The invention belongs to technical field of new energy material preparation, more particularly to a kind of produce in waste water from ferric phosphate to recycle phosphorus
The method of acid group and sulfate radical.
Background technique
Ferric phosphate is the main positive electrode of lithium ion battery, and preparation process mainly includes coprecipitation, hydro-thermal method etc..
Wherein, coprecipitation refers to that other compounds, which are added, precipitates ferric phosphate by after source of iron and phosphorus source (such as monoammonium phosphate) dissolution
It is precipitated, then phosphoric acid iron product is obtained by washing, dry, calcining.During coprecipitation prepares ferric phosphate, height can be generated
Concentration containing sulfate radicals (SO4 2-), phosphate radical (PO4 3-) and ammonia nitrogen (NH4- N) acid mother liquid.Existing processing ferric phosphate mother liquor
In ammonia nitrogen phosphate and sulfur, the polluters such as acid technique, not only complex process, operating cost are high, but also can not achieve in waste water
The resource utilization of valuable constituent, and then cause enterprise's production cost height, environmental protection pressure big.
Chinese patent application CN108975469A proposes a kind of substep removal ferric phosphate Phosphorus From Wastewater acid group and sulfate radical
Method, this method recycles most of phosphate radical in waste water in the form that ferric phosphate precipitates, but there are still phosphate radicals to recycle not
Thoroughly, ferric phosphate precipitates the problems such as purity not easy to control and hardly possible reuse.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
The method that kind recycles phosphate radical and sulfate radical from ferric phosphate production waste water.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A method of phosphate radical and sulfate radical are recycled from ferric phosphate production waste water, comprising the following steps:
(1) Ca (OH) is added into ferric phosphate mother liquor2, the first precipitation reaction is carried out, first is obtained by filtration after the reaction was completed
Precipitation slag and the first precipitated liquid；
(2) it is added into the first precipitated liquid after step (1) and contains ammonia solution, carry out the second precipitation reaction, after the reaction was completed
The second precipitation slag and the second precipitated liquid is obtained by filtration；
(3) the first precipitation slag after step (1) and the second precipitation slag after step (2) are mixed, obtains phosphogypsum；
Ferric phosphate mother liquor is mixed with phosphogypsum, carries out conversion reaction, conversion filtrate and calcium sulfate are obtained by filtration after the reaction was completed；
(4) the conversion filtrate after step (3) is back in step (1), makes the concentration of phosphate radical in precipitation reaction system
It maintains in a certain range, stops that ferric phosphate mother liquor is added into step (1), conversion filtrate substitution ferric phosphate mother liquor and and Ca
(OH)2Mixed precipitation obtains the first precipitation slag and the first precipitated liquid, repeats step (2) and (3) as procedure described above later；
(5) the second obtained precipitated liquid is mixed with acid solution, obtains neutralizing adjusting liquid；To neutralize adjust liquid sequentially into
Row is reverse osmosis, evaporation, crystallizes, and obtains ammonium sulfate solids and monoammonium phosphate solid.
Method of the invention, in step (1), ferric phosphate mother liquor (conversion filtrate) and Ca (OH)2It is main to occur such as formula (1) institute
The reaction shown:
Ca(OH)2+SO4 2-+2H+→CaSO4↓+2H2O formula (1)；
The main purpose of step (1) is the sulfate radical removed in ferric phosphate mother liquor (conversion filtrate), the first precipitation slag of gained
Mainly CaSO4, the first precipitated liquid mainly includes Ca2+、PO4 3-And NH4 +.The pH value that the first precipitation reaction need to be controlled is 4~5, when
Between be 0.5~2h；If the pH value of the first precipitation reaction is higher than 5, CaSO will lead to4With Ca3(PO4)2It precipitates simultaneously, ferric phosphate
The loss of phosphorus increases in mother liquor；If the pH value of the first precipitation reaction is lower than 4, CaSO will lead to4Precipitating is incomplete.
In step (2), the first precipitated liquid mainly occurs to react as shown in formula (2) with containing ammonia solution:
3Ca2++2PO4 3-+H++NH3·H2O→Ca3(PO4)2↓+NH4 ++H2O formula (2)；
The main purpose of step (2) is the calcium ion removed in the first precipitated liquid, and the second precipitation slag of gained is mainly Ca3
(PO4)2, the second precipitated liquid mainly includes PO4 3-And NH4 +.The pH value that the second precipitation reaction need to be controlled is 8.5~10, and the time is
0.5~2h；If the pH value of the second precipitation reaction is higher than 10, solubilised state Ca (OH) will lead to+Generation, be unfavorable for calcium ion
Removal, and will cause subsequent neutralization regulating step acid solution dosage and increase, increased costs；If the pH of the second precipitation reaction
Value is lower than 8.5, will lead to Ca3(PO4)2Not exclusively, calcium ion removal rate reduces precipitating.
In step (3), phosphogypsum is mainly by Ca3(PO4)2And CaSO4Composition, ferric phosphate mother liquor and phosphogypsum are main
Occur to react as shown in formula (3):
Ca3(PO4)2+6H++3SO4 2-→3CaSO4↓+2H3PO4Formula (3)；
The main purpose of step (3) is by the Ca in phosphogypsum3(PO4)2It is completely converted into calcium sulfate (CaSO4), simultaneously
By Ca3(PO4)2In PO4 3-All discharge into conversion filtrate.Converting the main component in filtrate includes SO4 2-、PO4 3-And NH4 +, conversion filtrate, which is all flowed back to be added in step (1), carries out the first precipitation reaction.Need to control conversion reaction pH value be 0.8~
1.5, the time is 0.5~2h；If the pH value of conversion reaction is higher than 1.5, the H of conversion is participated in+Concentration is too low, Ca3(PO4)2No
CaSO can be fully converted into4, cause the calcium sulfate slag purity decline obtained after conversion filtering；If the pH value of conversion reaction is lower than
0.8, then it needs to supplement basic agent into ferric phosphate mother liquor, increases reagent cost.
Above-mentioned method, it is furthermore preferred that in order to more thoroughly recycle sulfate radical and phosphate radical, while guaranteeing products obtained therefrom
Purity, in the step (1), the pH value of the first precipitation reaction of control is 4.5~5；In the step (2), the second precipitating of control
The pH value of reaction is 9~10；In the step (3), the pH value for controlling conversion reaction is 0.8~1.2.
Above-mentioned method, it is preferred that in terms of the volume of ferric phosphate mother liquor, phosphate concentration is 2 in the ferric phosphate mother liquor
~20g/L, sulfate concentration are 28.8~57.6g/L, and ammonia nitrogen concentration is 4.2~8.4g/L, and pH value is 0.8~1.2.
Above-mentioned method, it is preferred that it is described to prepare to obtain by ammonium hydroxide containing ammonia solution, or by ferric phosphate mother liquor and Ca
(OH)2Clear liquid after mixed precipitation obtains, and the pH value containing ammonia solution is 11~12.
Above-mentioned method, it is preferred that in the step (3), the liquid-solid ratio of ferric phosphate mother liquor and phosphogypsum is 5~
50m3/t.Liquid-solid ratio is lower than 5m3/ t then participates in the H of conversion+And SO4 2-Additional amount is insufficient, Ca3(PO4)2It cannot be fully converted into
CaSO4.It is furthermore preferred that the liquid-solid ratio of ferric phosphate mother liquor and phosphogypsum is 7.5~20m3/t。
Method of the invention, the second precipitated liquid is mixed with acid solution in step (5), is obtained neutralizing and is adjusted liquid.It neutralizes and adjusts
Saving step is subsequent reverse osmosis, evaporative crystallization steps preprocessing process.Neutralizing and adjusting liquid mainly includes PO4 3-、NH4 +And SO4 2-。
Compared with ferric phosphate mother liquor, SO in the ingredient for adjusting liquid is neutralized4 2-Concentration is lower, and pH value is higher.If directly to ferric phosphate mother liquor
Evaporative crystallization, then the sediment being precipitated is ammonium hydrogen sulfate, and if adjusting liquid evaporative crystallization to neutralizing, the sediment of precipitation is
Ammonium sulfate and monoammonium phosphate.Obviously, monoammonium phosphate product directly cannot be obtained to the crystallization of ferric phosphate mother liquid evaporation, can not realized
The recycling of phosphorus.
Above-mentioned method, it is preferred that the pH value for neutralizing adjusting liquid is 4~5.Neutralize adjust liquid pH value exceed or
It, all will be unfavorable to subsequent reverse osmosis and evaporative crystallization steps lower than the scope of the present invention.
Above-mentioned method, it is preferred that the evaporating temperature is 85~110 DEG C.By evaporating temperature control within the scope of this,
Advantageously reduce evaporation energy consumption.
Above-mentioned method, it is preferred that the crystallization temperature is 30~85 DEG C.It is molten when being coexisted according to ammonium sulfate with monoammonium phosphate
Solution degree variation with temperature trend (as shown in Figure 1) can be separately recovered to obtain pure by crystallization temperature control within the scope of this
Spend high ammonium sulfate solids and monoammonium phosphate solid.
Above-mentioned method, it is preferred that the acid solution is one of sulfuric acid, phosphoric acid, ferric phosphate mother liquor or a variety of, institute
Stating in ferric phosphate mother liquor phosphate concentration is 2~20g/L, and sulfate concentration is 28.8~57.6g/L, ammonia nitrogen concentration is 4.2~
8.4g/L, pH value are 0.8~1.2.
Compared with the prior art, the advantages of the present invention are as follows:
(1) method of the invention, technical concept is ingenious, and process route and process conditions are rationally, it can be achieved that Phosphorus From Wastewater is sour
Root and sulfate radical are kept completely separate；Wherein, phosphate radical is finally recycled in the form of monoammonium phosphate；Sulfate radical a part is converted to height
Purity calcium sulfate, a part are converted to ammonium sulfate.
(2) method of the invention, by control process conditions make the phosphate radical in the ferric phosphate mother liquor being initially added with
Liquid phase (PO4 3-)-solid phase (Ca3(PO4)2Precipitating)-liquid phase (PO4 3-) form circulation, finally fully enter the second precipitated liquid
In, avoid the loss of phosphorus in the operating process such as the first precipitation reaction, the second precipitation reaction and conversion reaction.
(3) method of the invention makes second to sink by carrying out neutralization adjusting, reverse osmosis, evaporative crystallization to the second precipitated liquid
Remaining sulfate radical is recycled in the form of pure ammonium sulfate solids in the liquid of shallow lake, and the rate of recovery of sulfate radical is 100%；Second is sunk simultaneously
Phosphate radical in the liquid of shallow lake is recycled in the form of monoammonium phosphate solid, and the rate of recovery of phosphate radical is 100%, efficiently solves existing skill
Phosphate radical recycles halfway problem in art.
(4) method of the invention, obtained monoammonium phosphate solid can prepare the phosphorus of ferric phosphate directly as coprecipitation
Source use, realize 100% reuse of phosphate radical, efficiently solve in the prior art by phosphate radical be converted into ferric phosphate precipitating but it is pure
The not easy to control and difficult direct reuse of degree is in the production the problem of.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the variation tendency of solubility with temperature when ammonium sulfate and monoammonium phosphate coexist；
Fig. 2 is the process flow diagram of the embodiment of the present invention 1；
Fig. 3 is the process flow diagram of comparative example 5 of the present invention；
Fig. 4 is the process flow diagram of comparative example 6 of the present invention.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of method of the invention recycling phosphate radical and sulfate radical from ferric phosphate production waste water, process flow signal
Figure is as shown in Figure 2, comprising the following steps:
(1) to 50L ferric phosphate mother liquor, (phosphate concentration 15.0g/L, sulfate concentration 48.0g/L, ammonia nitrogen concentration are
7.0g/L, pH value 1.1) in be added Ca (OH)2The first precipitation reaction is carried out, the pH value of the first precipitation reaction of control is 5, stirring
The first precipitation slag and the first precipitated liquid is obtained by filtration after mixing 2h；
(2) it is added into the first precipitated liquid after step (1) and carries out the second precipitating containing ammonia solution (10% ammonia spirit)
Reaction, the pH value of the second precipitation reaction of control are 10, and the second precipitation slag and the second precipitated liquid is obtained by filtration after being stirred 2h；
(3) the first precipitation slag after step (1) and the second precipitation slag after step (2) are mixed, obtains phosphogypsum；
By 50L ferric phosphate mother liquor and phosphogypsum mixing 2h, conversion reaction is carried out, the liquid-solid ratio of ferric phosphate mother liquor and phosphogypsum is
10m3/ t, the pH value for controlling mixed liquor in conversion process is 1.2, time 2h, and conversion filtrate is obtained by filtration after being stirred 2h
With 2.24kg calcium sulfate；
(4) the conversion filtrate after step (3) is all back in step (1), stops that ferric phosphate is added into step (1)
Mother liquor repeats step (1), (2) and (3)；
(5) the second obtained precipitated liquid is mixed with ferric phosphate mother liquor, obtains the neutralization that pH value is 5 and adjusts liquid；To neutralization
It adjusts liquid and sequentially carries out reverse osmosis, evaporation, crystallization, control evaporating temperature is 88 DEG C, and crystallization temperature is 60 DEG C, obtains 1.12kg sulphur
Sour ammonium solid and 0.90kg monoammonium phosphate solid.
Through detecting, the phosphate concentration in the second precipitated liquid is 15g/L, the process that phosphate radical is utilized in conversion filtrate cycle
Middle free of losses.The monoammonium phosphate solid purity that evaporative crystallization obtains is 99.7%, and monoammonium phosphate is up-to-standard, can be directly as
The phosphorus source that coprecipitation prepares ferric phosphate uses.Sulfate radical is then completely converted into 2.24kg calcium sulfate and 1.12kg ammonium sulfate,
The purity of middle calcium sulfate is 99.5%, and the purity of ammonium sulfate is 99.7%.
In operational process, reagent cost, byproduct income, cost of labor, power consumption cost (0.7 yuan/degree electricity) are comprehensively considered,
It handles 1 ton of ferric phosphate mother liquor and needs 17.1 yuan.
Embodiment 2:
It is a kind of it is of the invention from ferric phosphate production waste water in recycle phosphate radical and sulfate radical method, using with embodiment 1
The similar step of method, the difference from embodiment 1 is that: phosphate concentration is 5.4g/L in ferric phosphate mother liquor, and sulfate radical is dense
Degree is 25.5g/L, and ammonia nitrogen concentration 5.2g/L, the pH value of ferric phosphate mother liquor is 1.2；The pH value for controlling the first precipitation reaction is 4,
Being stirred the time is 0.5h；The pH value of second precipitation reaction is 9, and being stirred the time is 0.5h；It will obtain in step (5)
Second precipitated liquid is mixed with the sulfuric acid that mass concentration is 4%, is obtained the neutralization that pH is 4 and is adjusted liquid.
Through detecting, the phosphate concentration in the second precipitated liquid is 5.4g/L, the mistake that phosphate radical is utilized in conversion filtrate cycle
Free of losses in journey.The quality for the monoammonium phosphate solid that evaporative crystallization obtains is 0.37kg, purity 99.5%, monoammonium phosphate quality
Qualification, the phosphorus source that ferric phosphate can be prepared directly as coprecipitation use.Sulfate radical is then completely converted into 0.744kg calcium sulfate
With 1.04kg ammonium sulfate, wherein the purity of calcium sulfate is 99.6%, and the purity of ammonium sulfate is 99.7%.
Embodiment 3:
It is a kind of it is of the invention from ferric phosphate production waste water in recycle phosphate radical and sulfate radical method, using with embodiment 1
The similar step of method, the difference from embodiment 1 is that: phosphate concentration is 9.5g/L in ferric phosphate mother liquor, and sulfate radical is dense
Degree is 45.6g/L, and ammonia nitrogen concentration 6.2g/L, the pH value of ferric phosphate mother liquor is 0.9；Containing ammonia solution by ferric phosphate mother liquor and Ca
(OH)2Clear liquid after mixed precipitation obtains, and the pH value containing ammonia solution is 11.5, is added into the first precipitated liquid and contains ammonia solution, stirs
Mix mixing 1h.0.5h is mixed in phosphogypsum and 50L ferric phosphate mother liquor, the pH value for controlling mixed liquor in conversion process is
1.5, obtain conversion filtrate and calcium sulfate.
Through detecting, the phosphate concentration in the second precipitated liquid is 9.5g/L, the mistake that phosphate radical is utilized in conversion filtrate cycle
Free of losses in journey.The quality for the monoammonium phosphate solid that evaporative crystallization obtains is 0.58kg, purity 99.8%, monoammonium phosphate quality
Qualification, the phosphorus source that ferric phosphate can be prepared directly as coprecipitation use.Sulfate radical is then completely converted into 2.06kg calcium sulfate
With 1.13kg ammonium sulfate, wherein the purity of calcium sulfate is 99.5%, and the purity of ammonium sulfate is 99.7%.
Comparative example 1:
A method of phosphate radical and sulfate radical being recycled from ferric phosphate production waste water, using the method phase with embodiment 1
As step, the difference from embodiment 1 is that: control conversion process in mixed liquor pH value be 2.
Through detecting, the phosphate concentration in the second precipitated liquid is 12g/L, lower than phosphate concentration in ferric phosphate mother liquor, phosphorus
The acid group rate of recovery is 80%, monoammonium phosphate purity 99.6%.Sulfate radical is then converted to 1.42kg calcium sulfate and 1.375kg sulfuric acid
Ammonium, the rate of recovery of sulfate radical are 77.9%, and the purity of calcium sulfate is 87%, and the purity of ammonium sulfate is 99.7%.
Comparative example 2:
A method of phosphate radical and sulfate radical being recycled from ferric phosphate production waste water, using the method phase with embodiment 1
As step, the difference from embodiment 1 is that: in ferric phosphate mother liquor phosphate concentration be 15g/L, sulfate concentration 17.2g/
L, ammonia nitrogen concentration 2.5g/L, the pH value of ferric phosphate mother liquor are 1.1；The liquid-solid ratio of ferric phosphate mother liquor and phosphogypsum is 2m3/t。
Through detecting, the phosphate concentration in the second precipitated liquid is 8g/L, lower than phosphate concentration in ferric phosphate mother liquor, phosphoric acid
The root rate of recovery is 53%, monoammonium phosphate purity 99.5%.Sulfate radical is then converted to 0.41kg calcium sulfate and 0.59kg ammonium sulfate, sulphur
The rate of recovery of acid group is 80.2%, and the purity of calcium sulfate is 89%, and the purity of ammonium sulfate is 99.6%.
Comparative example 3:
A method of phosphate radical and sulfate radical being recycled from ferric phosphate production waste water, using the method phase with embodiment 1
As step, the difference from embodiment 1 is that: in ferric phosphate mother liquor phosphate concentration be 15g/L, sulfate concentration 17.2g/
L, ammonia nitrogen concentration 2.5g/L, the pH value of ferric phosphate mother liquor are 1.1；The pH value for controlling the second precipitation reaction is 7.
Through detecting, the calcium ion concentration in the second precipitated liquid is 200mg/L, and calcium ion concentration is excessively high in the second precipitated liquid,
It cannot directly enter reverse osmosis process, phosphate radical, sulfate radical can not achieve recycling.
Comparative example 4:
A method of phosphate radical and sulfate radical being recycled from ferric phosphate production waste water, using the method phase with embodiment 1
As step, the difference from embodiment 1 is that: in ferric phosphate mother liquor phosphate concentration be 15g/L, sulfate concentration 17.2g/
L, ammonia nitrogen concentration 2.5g/L, the pH value of ferric phosphate mother liquor are 1.1；Crystallization temperature is 25 DEG C.
The quality for the monoammonium phosphate solid that evaporative crystallization obtains is 0.48kg, and purity 80%, the phosphate radical rate of recovery is
51.2%.Sulfate radical is then converted to 0.28kg calcium sulfate and 0.43kg ammonium sulfate, and the sulfate radical rate of recovery is 55.8%, wherein sulfuric acid
The purity of calcium is 99.6%, and the purity of ammonium sulfate is 89.7%.
Comparative example 5:
A method of recycling phosphate radical and sulfate radical from ferric phosphate production waste water, process flow chart as shown in figure 3,
To 50L ferric phosphate mother liquor, (phosphate concentration 15g/L, sulfate concentration 17.2g/L, ammonia nitrogen concentration 2.5g/L, pH value are
1.1) Ca (OH) is added in2Neutralization-precipitation reaction is carried out, control neutralization precipitation pH is 5, is stirred 2h, obtains neutralization precipitation slag
With neutralization precipitation liquid.It neutralizes adjusting liquid and sequentially carries out reverse osmosis, evaporation, crystallization, obtain ammonium sulfate solids and monoammonium phosphate solid.
The quality for the monoammonium phosphate solid that evaporative crystallization obtains is 0.36kg, and purity 80%, the phosphate radical rate of recovery is
32%.Sulfate radical is then converted to 0.291kg calcium sulfate and 0.189kg ammonium sulfate, and retrieval of sulfuric acid rate is 32.6%, wherein calcium sulfate
Purity be 79.6%, the purity of ammonium sulfate is 84.7%.
Comparative example 6:
A method of recycling phosphate radical and sulfate radical from ferric phosphate production waste water, process flow chart as shown in figure 4,
To 50L ferric phosphate mother liquor, (phosphate concentration 15g/L, sulfate concentration 17.2g/L, ammonia nitrogen concentration 2.5g/L, pH value are
1.1) ammonium hydroxide is added in and carries out neutralization adjusting, controlling and neutralizing adjusting pH is 5, is stirred 2h, obtains neutralizing adjusting liquid.It neutralizes and adjusts
Section liquid sequentially carries out reverse osmosis, evaporation, crystallization, obtains ammonium sulfate solids and monoammonium phosphate solid.
The quality for the monoammonium phosphate solid that evaporative crystallization obtains is 0.91kg, and purity 99.6%, the phosphate radical rate of recovery is
100%.Sulfate radical is then converted to 1.18kg ammonium sulfate, and retrieval of sulfuric acid rate is 100%, and the purity of ammonium sulfate is 99.7%.
In operational process, reagent cost, byproduct income, cost of labor, power consumption cost (0.7 yuan/degree electricity) are comprehensively considered,
It handles 1 ton of ferric phosphate mother liquor and needs 29.5 yuan.
In conjunction with the embodiments 1 and comparative example 1~2 it is found that will precipitating and conversion process the conditions control such as pH, liquid-solid ratio at this
In the range of invention, 100% reuse of phosphorus can may be implemented to avoid the loss of phosphate radical in ferric phosphate mother liquor.
In conjunction with the embodiments 1 and comparative example 3 it is found that within the scope of the invention by the control of the pH value of the second precipitation reaction, can
To avoid causing in the second precipitated liquid, calcium ion concentration is excessively high, cannot directly enter the phenomenon that reverse osmosis process.Also, if not
The pH value of the second precipitation reaction is controlled, but increases decalcification pretreatment newly before reverse osmosis process, it will leads to integrated operation cost
It greatly increases.
In conjunction with the embodiments 1 and comparative example 4 it is found that crystallization temperature need to be controlled within the scope of the invention, otherwise phosphoric acid one
Ammonium product can be mixed with ammonium sulfate, and monoammonium phosphate cannot function as the phosphorus source use that coprecipitation prepares ferric phosphate.
In conjunction with the embodiments 1 and comparative example 5 it is found that the present invention rationally designs process route, by by Ca (OH)2With ferric phosphate
Neutralization precipitation slag reuse after mother liquor neutralization precipitation, effectively prevents a large amount of losses of phosphate radical in ferric phosphate mother liquor；The present invention
Method industrial value it is high, be suitable for industrial applications.
In conjunction with the embodiments 1 and comparative example 6 it is found that since ammonium hydroxide cost is significantly higher than Ca (OH)2And a large amount of NH3Addition
Cause neutralize adjust liquid salt content increase, directly into ferric phosphate mother liquor directly plus ammonium hydroxide, again to neutralize adjust liquid it is reverse osmosis
The processing mode of processing and evaporative crystallization, will lead to reverse osmosis and evaporation and crystal process increased costs, and integrated operation cost is significant
Increase, and method of the invention, operating cost is effectively controlled, productivity effect has been combined.
Claims (10)
1. a kind of method for recycling phosphate radical and sulfate radical from ferric phosphate production waste water, which comprises the following steps:
(1) Ca (OH) is added into ferric phosphate mother liquor2, the first precipitation reaction is carried out, the first precipitation slag is obtained by filtration after the reaction was completed
With the first precipitated liquid；
(2) it is added into the first precipitated liquid after step (1) and contains ammonia solution, carried out the second precipitation reaction, filter after the reaction was completed
Obtain the second precipitation slag and the second precipitated liquid；
(3) the first precipitation slag after step (1) and the second precipitation slag after step (2) are mixed, obtains phosphogypsum；By phosphorus
Sour iron mother liquor is mixed with phosphogypsum, carries out conversion reaction, and conversion filtrate and calcium sulfate are obtained by filtration after the reaction was completed；
(4) the conversion filtrate after step (3) is back in step (1), stops that ferric phosphate mother liquor is added into step (1), weight
Multiple step (1), (2) and (3)；
(5) the second obtained precipitated liquid is mixed with acid solution, obtains neutralizing adjusting liquid；It is sequentially carried out instead to adjusting liquid is neutralized
Infiltration, evaporation, crystallization, obtain ammonium sulfate solids and monoammonium phosphate solid.
2. the method according to claim 1, wherein controlling the pH value of the first precipitation reaction in the step (1)
It is 4~5；In the step (2), the pH value of the second precipitation reaction of control is 8.5~10；In the step (3), control conversion is anti-
The pH value answered is 0.8~1.5.
3. according to the method described in claim 2, it is characterized in that, controlling the pH value of the first precipitation reaction in the step (1)
It is 4.5~5；In the step (2), the pH value of the second precipitation reaction of control is 9~10；In the step (3), control conversion is anti-
The pH value answered is 0.8~1.2.
4. method according to claim 1,2 or 3, which is characterized in that in the step (1), (2) and (3), control reaction
Time be 0.5~2h.
5. method according to claim 1,2 or 3, which is characterized in that in terms of the volume of ferric phosphate mother liquor, the ferric phosphate
Phosphate concentration is 2~20g/L in mother liquor, and sulfate concentration is 28.8~57.6g/L, and ammonia nitrogen concentration is 4.2~8.4g/L, pH
Value is 0.8~1.2.
6. method according to claim 1,2 or 3, which is characterized in that it is described to prepare to obtain by ammonium hydroxide containing ammonia solution, or
By ferric phosphate mother liquor and Ca (OH)2Clear liquid after mixed precipitation obtains, and the pH value containing ammonia solution is 11~12.
7. method according to claim 1,2 or 3, which is characterized in that in the step (3), ferric phosphate mother liquor with it is phosphorous
The liquid-solid ratio of gypsum is 5~50m3/t。
8. method according to claim 1,2 or 3, which is characterized in that the pH value for neutralizing adjusting liquid is 4~5.
9. method according to claim 1,2 or 3, which is characterized in that the evaporating temperature is 85~110 DEG C, the knot
Brilliant temperature is 30~85 DEG C.
10. method according to claim 1,2 or 3, which is characterized in that the acid solution is sulfuric acid, phosphoric acid, ferric phosphate
One of mother liquor is a variety of.
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