CN107445139B - The circulation utilization method of mother liquor in a kind of ferric phosphate production process - Google Patents
The circulation utilization method of mother liquor in a kind of ferric phosphate production process Download PDFInfo
- Publication number
- CN107445139B CN107445139B CN201710856857.7A CN201710856857A CN107445139B CN 107445139 B CN107445139 B CN 107445139B CN 201710856857 A CN201710856857 A CN 201710856857A CN 107445139 B CN107445139 B CN 107445139B
- Authority
- CN
- China
- Prior art keywords
- ferric phosphate
- mother liquor
- reaction
- production process
- circulation utilization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention discloses a kind of circulation utilization methods of mother liquor in ferric phosphate production process, comprising the following steps: first by ferric phosphate reaction raw materials liquid and H2O2Reaction kettle is added and carries out ferric phosphate synthesis, obtains ferric phosphate slurry and mother liquor after synthetic reaction and pulp filters pressing, then respectively by mother liquor phosphorus and ammonium recycled in the form of ferric phosphate filter cake and monoammonium phosphate solution, and fully recovering is into ferric phosphate synthesis step.Method provided by the invention can make full use of the useful components such as remaining nitrogen, phosphorus in mother liquor, avoid the wasting of resources, the overall cost and mating environmentally friendly cost of ferric phosphate production is greatly reduced by recycling ferric phosphate mother liquor regeneration produced during the preparation process.
Description
Technical field
The invention belongs to technical field of new energy material preparation, particularly, are related to mother liquor in a kind of ferric phosphate production process
Circulation utilization method.
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 from
Sub- battery is widely used to all kinds of movements because of the advantages that its voltage is high, energy density is big, good cycle, hot properties are good
In communication apparatus, the vehicles.Currently, the positive electrode of lithium ion battery mainly uses ferric phosphate.The system of traditional ferric phosphate
Standby technique 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 can obtain ferric phosphate product.During traditional co-precipitation method prepares ferric phosphate, generate a large amount of
Nitrogenous, phosphorus waste mother liquor.Existing production technology is not only unable to the useful component in reuse mother liquor, and need using it is complicated,
Expensive technique is effectively treated the pollutants such as nitrogen, phosphorus, acid in mother liquor, causes the serious wasting of resources and enterprise raw
Produce the increase of cost, environmental protection pressure.
Summary of the invention
It is an object of that present invention to provide a kind of circulation utilization methods of mother liquor in ferric phosphate production process, to solve existing skill
When preparing ferric phosphate using coprecipitation in art, the technology of environmental pollution caused by produced mother liquor and nitrogen, phosphor resource waste is asked
Topic.
To achieve the above object, the present invention provides a kind of circulation utilization methods of mother liquor in ferric phosphate production process: will
NH4H2PO4、FeSO4、H3PO4And H2O2Reaction kettle is added, ferric phosphate filter cake and phosphoric acid are obtained after synthetic reaction, pulp and filters pressing
Iron mother liquor；Ferric phosphate filter cake is used to prepare phosphoric acid iron product, and ferric phosphate mother liquor is mainly by NH4HSO4And H3PO4Composition.Described
Ferric phosphate mother liquid recycling method the following steps are included:
1) P resource recycles in ferric phosphate mother liquor: (1) according to a certain percentage by FeSO4、H2O2And H2SO4Mixing is simultaneously
Oxidation reaction is carried out, ferric sulfate material liquid is obtained；(2) the ferric phosphate mother liquor and step (1) are obtained according to a certain percentage
Ferric sulfate material liquid mixes and carries out the first reaction, while the pH value of the first reaction system is adjusted with ammonia, obtains the first reaction slurry
Material；The first filters pressing filter cake and the first filtrate are obtained after (3) first reaction paste filters pressings, by the first filters pressing filter cake, H2O and H3PO4It presses
Certain proportion mixing carries out the second reaction, obtains ferric phosphate slurry；(4) the ferric phosphate slurry that step (3) obtains is through the second filters pressing
Afterwards, ferric phosphate filter cake and the second filtrate are obtained；By obtained ferric phosphate filter cake fully recovering into ferric phosphate synthesis step；
2) N resource recycles in ferric phosphate mother liquor: (1) collecting the first filtrate and the second filtrate to obtain mixing filter
Lime white is added in Xiang Suoshu mixed filtrate and adjusts mixed filtrate pH for liquid；(2) stripping processing is carried out to the mixed filtrate, blown
The part ammonia of mid-career student enters the first reaction, and remaining ammonia is absorbed by phosphoric acid, obtains NH4H2PO4Solution；It (3) will be described
NH4H2PO4All flow back the raw material produced as ferric phosphate.
The circulation utilization method of mother liquor in the ferric phosphate production process: in the reaction system of production phosphoric acid iron product
NH4H2PO4Mass concentration be 5%~8%, FeSO4Mass concentration be 7%~10%, H3PO4Mass concentration be 0.5%
~0.8%, H2O2Mass concentration be 0.8%~1.2%.
The circulation utilization method of mother liquor in the ferric phosphate production process: the ferric phosphate mother liquor contains NH4HSO4With
H3PO4Composition；The mass concentration of ammonia nitrogen is 5~12g/L in the ferric phosphate mother liquor, and the mass concentration of phosphorus is 5~15g/L.
The circulation utilization method of mother liquor in the ferric phosphate production process: (1) described oxidation reaction is added in step 1)
H2O2With FeSO4Molar ratio be 1.2:1~2:1, the H that the oxidation reaction is added2SO4With FeSO4Molar ratio be 1:20
~1:5.
The circulation utilization method of mother liquor in the ferric phosphate production process: (2) described first reaction is added in step 1)
Ferric sulfate material liquid in Fe and mother liquor in H3PO4Molar ratio be 1:1~1.2:1, it is described first reaction pH be 2~4.
The circulation utilization method of mother liquor in the ferric phosphate production process: (3) second reaction controlling in step 1)
First filters pressing filter cake and H2O mass ratio is 1:5~1:20, controls H3PO4And H2O mass ratio is 1:30~1:10.
The circulation utilization method of mother liquor in the ferric phosphate production process: the time of the oxidation reaction be 0.7~
The time of 1.5h, first reaction are 0.5~1h, and the time of second reaction is 3~4h.
The circulation utilization method of mother liquor in the ferric phosphate production process: the temperature of the oxidation reaction is 40~60
DEG C, the temperature of first reaction is 40~60 DEG C, and the temperature of second reaction is 80~90 DEG C.
The circulation utilization method of mother liquor in the ferric phosphate production process: mixed during (2) described stripping in step 2)
The pH for closing filtrate is 11~13；The H being added in (3) described absorption process in step 2)3PO4Concentration is 1.5~2.5mol/L.
The invention has the following advantages:
Method provided by the invention is handled by the way that traditional co-precipitation method is prepared the mother liquor regeneration generated during ferric phosphate,
And all recycle gained ferric phosphate reaction raw materials liquid, on the one hand take full advantage of remaining nitrogen and phosphorus etc. in mother liquor
Useful component avoids the wasting of resources, and effectively reduces the production cost of ferric phosphate；On the other hand reduce nitrogenous and phosphorus
The generation and discharge of acid waste water, greatly reduce the environmentally friendly auxiliary facility of traditional phosphoric acid process for making iron investment and operation at
This.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
Below with reference to figure, the present invention is described in further detail.
Detailed description of the invention
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the process flow diagram of the preferred embodiment of the present invention and comparative example 1~4；
Fig. 2 is the process flow diagram of comparative example 5；
Fig. 3 is the XRD diagram of phosphoric acid iron product in the embodiment of the present invention 1.
Specific embodiment
The embodiment of the present invention is described in detail below in conjunction with attached drawing, but the present invention can be defined by the claims
Implement with the multitude of different ways of covering.
Referring to Fig. 1, the first step carries out the synthesis of ferric phosphate, by ferric phosphate reaction raw materials liquid and H2O2Reaction kettle is added, occurs
Synthetic reaction, reaction equation are as follows:
2NH4H2PO4+2FeSO4+H2O2=2FePO4+2NH4HSO4+2H2O (1)
Ferric phosphate reaction raw materials liquid is by NH4H2PO4、FeSO4、H3PO4It forms, the NH in reaction raw materials liquid4H2PO4、FeSO4
With H2O2Redox reaction occurs, generates FePO4Precipitating and NH4HSO4；H in reaction raw materials liquid3PO4Reaction is not participated in directly,
Its main function is the acidity for adjusting reaction process.The temperature for controlling synthetic reaction is 80~90 DEG C.
By the concentration of each ingredient in control reaction raw materials liquid aqueous solution, guarantee the stabilization of ferric phosphate product quality.Reaction
The concentration of each ingredient requires as follows in material liquid: NH4H2PO4Mass concentration be 5%~8%, FeSO4Mass concentration be 7%
~10%, H3PO4Mass concentration be 0.5%~0.8%.Participate in the H of synthetic reaction2O2Mass concentration be 0.8%~
1.2%.
Pulp filters pressing obtains ferric phosphate filter cake and mother liquor；Ferric phosphate filter cake obtains ferric phosphate by processes such as dry, calcinings
Product；Mother liquor is by NH4HSO4、H3PO4Deng composition, NH in mother liquor4 +Mass concentration be 5~12g/L, PO4 3-Mass concentration be 5
~15g/L.
Second step recycles the phosphorus in mother liquor, according to a certain percentage by FeSO4、H2O2And H2SO4Oxidation reaction is mixed and carries out,
Oxidation reaction material liquid is obtained, reaction equation is as follows:
2FeSO4+H2SO4+3H2O2=Fe2(SO4)3+4H2O+O2↑ (2)
In order to guarantee that the concentration of each ingredient of oxidation reaction material liquid meets the preparation requirement of the ferric phosphate, H is controlled2O2With
FeSO4Molar ratio be 1.2:1~2:1, oxidation reaction be added H2SO4With FeSO4Molar ratio be 1:20~1:5.Oxidation is anti-
The temperature answered is 40~60 DEG C, and the time of oxidation reaction is 0.7~1.5h.
Mother liquor is mixed progress first with oxidation reaction material liquid according to a certain percentage to react, controls oxidation reaction material liquid
In Fe and mother liquor in H3PO4Molar ratio be 1:1~1.2:1, the reaction time is 0.5~1h, and the pH of reaction is 2~4.First
The first filters pressing filter cake is obtained after the hydraulic filter of reaction raw materials.
To guarantee ferric phosphate product quality, needs to carry out autoclaving conversion to ferric phosphate filter cake, convert di iron to
Ferric phosphate.By the first filters pressing filter cake and H2O、H3PO4It is mixed in a certain ratio the second reaction of progress, obtains ferric phosphate slurry；Control
First filters pressing filter cake and H2O mass ratio is 1:5~1:20, controls H3PO4And H2The mass ratio of O is 1:30~1:10, the second reaction
Time be 3~4h, second reaction temperature be 80~90 DEG C.
Ferric phosphate slurry obtains ferric phosphate filter cake and fully recovering into ferric phosphate synthesis step after the second filters pressing.
Third step recycles the ammonium in mother liquor, collects the first filtrate and the second filtrate to obtain mixed filtrate, to mixed filtrate
Middle addition lime white adjusts mixed filtrate pH to 11~13；Stripping processing, the part ammonia that stripping generates are carried out to mixed filtrate
Into the first reaction, remaining ammonia is absorbed by phosphoric acid, and absorption obtains NH4H2PO4Solution；In order to guarantee NH4H2PO4Solution concentration with
The component requirements of ferric phosphate reaction raw materials liquid match, and it is 1.5~2.5mol/L that control, which absorbs phosphoric acid concentration used,；By NH4H2PO4
Component part fully recovering as ferric phosphate reaction raw materials liquid is into ferric phosphate synthesis step.
Embodiment
Material and instrument used are commercially available in following embodiment.
Embodiment 1
Technique shown in Figure 1 prepares phosphoric acid iron product.By ferric phosphate reaction raw materials liquid and H2O2Reaction kettle is added, carries out
Synthetic reaction, ferric phosphate reaction raw materials liquid is by NH4H2PO4、FeSO4、H3PO4Composition, the concentration of each ingredient is such as in reaction raw materials liquid
Under: NH4H2PO4Mass concentration be 5.3%, FeSO4Mass concentration be 7.0%, H3PO4Mass concentration be 0.6%.It participates in
The H of synthetic reaction2O2Mass concentration be 0.8%.The temperature for controlling synthetic reaction is 80 DEG C.
Phosphorus concentration in pulp filters pressing post mother liquor is 9.8g/L, ammonia nitrogen concentration 8g/L.
To the FeSO of volume 50L, concentration 260g/L4The H of volume 14.7L, concentration 27% are added in solution2O2And volume
The H of 0.46L, concentration 98%2SO4It mixes and carries out oxidation reaction, H2O2With FeSO4Molar ratio be 1.5:1, H2SO4With FeSO4
Molar ratio be 1:10, reaction temperature be 60 DEG C, reaction time 50min obtains oxidation reaction material liquid.
Hybrid reaction in 800L mother liquor, Fe and mother liquor in oxidation reaction material liquid is all added in oxidation reaction material liquid
Middle H3PO4Molar ratio be 1:1, reaction time 1h, reaction temperature be 55 DEG C, reaction pH be 2.
The feed liquid filters pressing that reaction generates obtains the first filters pressing filter cake.Control the first filters pressing filter cake, H2O and H3PO4Mass ratio
The second reaction is carried out for 1:10:0.5, the second reaction time was 3h, and the second reaction temperature is 90 DEG C.The phosphoric acid that second reaction generates
Iron slurry obtains ferric phosphate filter cake and fully recovering into ferric phosphate synthesis step after filters pressing.
After expansion drying and calcination processing, the phosphoric acid iron product of 950g qualification, phosphorus have been prepared from 800L mother liquor
The rate of recovery be 85%, Fe/P molar ratio is 0.97 in product, and the XRD spectrum of product is as shown in figure 3, realize phosphorus in mother liquor
It recycles.
It collects the first filtrate and the second filtrate to obtain mixed filtrate, lime white is added into mixed filtrate and adjusts mixing filter
Liquid pH to 13；Stripping processing is carried out to mixed filtrate, the ammonia that stripping goes out is absorbed with the phosphoric acid of 2mol/L, obtains NH4H2PO4
Solution.
After stripping and absorption processing, recycling has obtained the suitable NH of concentration from 800L mother liquor4H2PO4(it is converted to dry weight
51kg), the rate of recovery of ammonia nitrogen reaches 96%, the NH of recycling4H2PO4Component part reuse as ferric phosphate reaction raw materials liquid is extremely
In ferric phosphate synthesis step.
Embodiment 2
The difference from embodiment 1 is that the concentration of each ingredient is as follows in reaction raw materials liquid: NH4H2PO4Mass concentration be
7.6%, FeSO4Mass concentration be 10.0%, H3PO4Mass concentration be 0.8%.Participate in the H of synthetic reaction2O2Quality it is dense
Degree is 1.1%.The temperature for controlling synthetic reaction is 90 DEG C.
H in oxidation reaction2O2With FeSO4Molar ratio be 1.2:1, first reaction pH be 3.Lime is added during stripping
Slurry adjusts mixed filtrate pH to 11.
After expansion drying and calcination processing, the phosphoric acid iron product of 1050g qualification, phosphorus have been prepared from 800L mother liquor
The rate of recovery be 95%；After stripping and absorption processing, recycling has obtained the suitable NH of concentration from 800L mother liquor4H2PO4(folding
It is counted as dry weight 48kg), the rate of recovery of ammonia nitrogen reaches 90%, realizes the recycling of phosphorus and ammonium in mother liquor.
Embodiment 3
The difference from embodiment 1 is that H in oxidation reaction2SO4With FeSO4Molar ratio be 1:20, reaction temperature 40
DEG C, reaction time 90min.H in Fe and mother liquor in oxidation reaction material liquid3PO4Molar ratio be 1.2:1, reaction pH be 4.
First filters pressing filter cake, H2O and H3PO4Mass ratio be 0.5:10:0.33 carry out second reaction, the second reaction temperature
It is 80 DEG C.The ammonia that stripping goes out is absorbed with the phosphoric acid of 2.5mol/L.
After expansion drying and calcination processing, the phosphoric acid iron product of 1060g qualification, phosphorus have been prepared from 800L mother liquor
The rate of recovery be 96%, after stripping and absorption processing, recycling has obtained the suitable NH of concentration from 800L mother liquor4H2PO4(folding
It is counted as dry weight 51kg), the rate of recovery of ammonia nitrogen reaches 96%, realizes the recycling of phosphorus and ammonium in mother liquor.
Embodiment 4
The difference from embodiment 1 is that H in oxidation reaction2SO4With FeSO4Molar ratio be 1:5, H2O2With FeSO4Rub
You are than being 1.2:1.
First filters pressing filter cake, H2O and H3PO4Mass ratio be 2:10:1 carry out second reaction.With the phosphoric acid pair of 1.5mol/L
The ammonia that stripping goes out absorbs.
After expansion drying and calcination processing, the phosphoric acid iron product of 980g qualification, phosphorus have been prepared from 800L mother liquor
The rate of recovery be 88%, after stripping and absorption processing, recycling has obtained the suitable NH of concentration from 800L mother liquor4H2PO4Product
The rate of recovery of (being converted to dry weight 52kg), ammonia nitrogen reaches 97%, realizes the recycling of phosphorus and ammonium in mother liquor.
Comparative example 1
The difference from embodiment 1 is that H in oxidation reaction2SO4With FeSO4Molar ratio be 1:50.
Due to H in oxidation reaction2SO4Dosage is insufficient, and reaction equation (2) carries out insufficient, FeSO4Fail to be completely oxidized to Fe3
(SO4)2, cause the transformation efficiency of ferric phosphate in the first reaction and the second reaction lower, phosphorous recovery is only 47%, anti-from 800L
Answer the phosphoric acid iron product that 520g qualification has been prepared in material liquid.
Comparative example 2
The difference from embodiment 1 is that the first filters pressing filter cake of control and H2O、H3PO4Mass ratio be that 1:2:0.04 carries out the
Two reactions.
Due to filter cake and H in the second reaction2The mass ratio of O is too small, filter cake and H2The slurry concentration that O is formed is excessively high, leads to the
Two reactions carry out insufficient.Due to H2O、H3PO4Mass ratio it is excessively high, slurry acidity is too low, leads to the di iron in slurry
It can not be fully converted to ferric phosphate.Contain di iron, product matter from the product being prepared in 800L reaction raw materials liquid
It measures unqualified.
Comparative example 3
The difference from embodiment 1 is that the temperature of the second reaction of control is 50 DEG C.
Since the second reaction temperature is too low, the di iron in slurry can not be fully converted to ferric phosphate, through this technique
The indexs such as the phosphoric acid iron product crystalline form and performance that are prepared after processing are unqualified.
Comparative example 4
The difference from embodiment 1 is that being absorbed with the phosphoric acid of 0.2mol/L to the ammonia that stripping goes out.
Since phosphoric acid concentration is too low, cause to absorb obtained NH4H2PO4Concentration of polymer solution is unsatisfactory for ferric phosphate material liquid
Requirement, NH4H2PO4Solution can not reuse.
It is by comparative example 1~4 it is found that anti-if not controlling synthetic reaction in this technique, oxidation reaction, the first reaction and second
The technological parameter answered not can guarantee the rate of recovery and quality of phosphoric acid iron product then, be unable to control the NH that recycling obtains4H2PO4Solution
Quality, but in the process parameters range of the claims in the present invention description, it is attained by the ideal rate of recovery and quality.
Comparative example 5
Technique shown in Figure 2 prepares phosphoric acid iron product.By ferric phosphate reaction raw materials liquid and H2O2Reaction kettle is added, occurs
Synthetic reaction, ferric phosphate reaction raw materials liquid is by NH4H2PO4、FeSO4、H3PO4Composition, the concentration of each ingredient is such as in reaction raw materials liquid
Under: NH4H2PO4Mass concentration be 5.3%, FeSO4Mass concentration be 7.0%, H3PO4Mass concentration be 0.6%.It participates in
The H of first reaction2O2Mass concentration be 0.8%.The temperature for controlling synthetic reaction is 80 DEG C.
Mixed liquor after synthetic reaction obtains ferric phosphate filter cake and mother liquor after pulp and filters pressing；Lime is added into mother liquor
Precipitation reaction occurs, the phosphate radical in mother liquor is transformed into calcium phosphate removing；Mother liquor after dephosphorization is using stripping and oxychloride
Group technology processing, by the ammonia nitrogen removal in mother liquor；Mother liquor pH after adjusting denitrogenation guarantees standard water discharge discharge.
As comparative example 5 it is found that if preparing ferric phosphate using technique shown in Fig. 2, ferric phosphate mother liquor can not reuse, and need
The techniques such as newly-increased dephosphorization, denitrogenation, pH adjusting carry out processing up to standard to mother liquor, and the cost of every processing 1t mother liquor reaches 20 yuan or more.
And the present invention has recycled most of phosphor resource in mother liquor, it is ensured that the first and second filtrate treating capacities are reduced, and processing cost is substantially
Degree is reduced, further more, nitrogen and phosphor resource largely recycle in ferric phosphate mother liquor, is increased ferric phosphate yield, is reduced simultaneously
NH4H2PO4Dosage, remarkable in economical benefits.The cost of the every processing 1t mixed filtrate of the present invention only has 10 yuan.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. the circulation utilization method of mother liquor in a kind of ferric phosphate production process, by NH4H2PO4、FeSO4、H3PO4And H2O2It is added anti-
Kettle is answered, ferric phosphate filter cake and ferric phosphate mother liquor are obtained after synthetic reaction, pulp and filters pressing；Ferric phosphate filter cake is used to prepare phosphoric acid
Iron product, ferric phosphate mother liquor is mainly by NH4HSO4And H3PO4Composition；It is characterized in that, the ferric phosphate mother liquid recycling
Method the following steps are included:
1) P resource recycles in ferric phosphate mother liquor: (1) according to a certain percentage by FeSO4、H2O2And H2SO4It mixes and carries out
Oxidation reaction obtains ferric sulfate material liquid；(2) sulfuric acid for according to a certain percentage obtaining the ferric phosphate mother liquor and step (1)
Iron material liquid mixes and carries out the first reaction, while the pH value of the first reaction system is adjusted with ammonia, obtains the first reaction paste；
The first filters pressing filter cake and the first filtrate are obtained after (3) first reaction paste filters pressings, by the first filters pressing filter cake and H2O、H3PO4By one
Certainty ratio mixing carries out the second reaction, obtains ferric phosphate slurry；(4) the ferric phosphate slurry that step (3) obtains is after the second filters pressing,
Obtain ferric phosphate filter cake and the second filtrate；By obtained ferric phosphate filter cake fully recovering into ferric phosphate synthesis step；
2) N resource recycles in ferric phosphate mother liquor: (1) it collects first filtrate and second filtrate to obtain mixed filtrate, to
Lime white is added in the mixed filtrate and adjusts mixed filtrate pH；(2) stripping processing is carried out to the mixed filtrate, stripping generates
Part ammonia enter the first reaction, remaining ammonia absorbed by phosphoric acid, obtains NH4H2PO4Solution；(3) by the NH4H2PO4Entirely
Flow back the raw material produced as ferric phosphate in portion.
2. the circulation utilization method of mother liquor in ferric phosphate production process according to claim 1, which is characterized in that production phosphorus
NH in the reaction system of sour iron product4H2PO4Mass concentration be 5%~8%, FeSO4Mass concentration be 7%~10%,
H3PO4Mass concentration be 0.5%~0.8%, H2O2Mass concentration be 0.8%~1.2%.
3. the circulation utilization method of mother liquor in ferric phosphate production process according to claim 1 or 2, which is characterized in that institute
It states ferric phosphate mother liquor and contains NH4HSO4And H3PO4；The mass concentration of ammonia nitrogen is 5~12g/L, the matter of phosphorus in the ferric phosphate mother liquor
Amount concentration is 5~15g/L.
4. the circulation utilization method of mother liquor in ferric phosphate production process according to claim 1, which is characterized in that step 1)
In the H that is added of (1) described oxidation reaction2O2With FeSO4Molar ratio be 1.2:1~2:1, the H that the oxidation reaction is added2SO4
With FeSO4Molar ratio be 1:20~1:5.
5. the circulation utilization method of mother liquor in ferric phosphate production process according to claim 1, which is characterized in that step 1)
In (2) it is described first reaction be added ferric sulfate material liquid in Fe and mother liquor in H3PO4Molar ratio be 1:1~1.2:1, institute
The pH for stating the first reaction is 2~4.
6. the circulation utilization method of mother liquor in ferric phosphate production process according to claim 1, which is characterized in that step 1)
In (3) described second reaction controlling the first filters pressing filter cake and H2O mass ratio is 1:5~1:20, controls H3PO4And H2The mass ratio of O
For 1:30~1:10.
7. the circulation utilization method of mother liquor in ferric phosphate production process according to claim 1, which is characterized in that the oxygen
Change reaction time be 0.7~1.5h, it is described first reaction time be 0.5~1h, it is described second reaction time be 3~
4h。
8. the circulation utilization method of mother liquor in ferric phosphate production process according to claim 1 or claim 7, which is characterized in that institute
The temperature for stating oxidation reaction is 40~60 DEG C, and the temperature of first reaction is 40~60 DEG C, and the temperature of second reaction is
80~90 DEG C.
9. the circulation utilization method of mother liquor in ferric phosphate production process according to claim 1, which is characterized in that described to blow
The pH of mixed filtrate is 11~13 during de-；The H being added in the absorption process3PO4Concentration is 1.5~2.5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710856857.7A CN107445139B (en) | 2017-09-21 | 2017-09-21 | The circulation utilization method of mother liquor in a kind of ferric phosphate production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710856857.7A CN107445139B (en) | 2017-09-21 | 2017-09-21 | The circulation utilization method of mother liquor in a kind of ferric phosphate production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107445139A CN107445139A (en) | 2017-12-08 |
| CN107445139B true CN107445139B (en) | 2019-10-29 |
Family
ID=60497093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710856857.7A Active CN107445139B (en) | 2017-09-21 | 2017-09-21 | The circulation utilization method of mother liquor in a kind of ferric phosphate production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107445139B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109264744A (en) * | 2018-10-19 | 2019-01-25 | 湖南雅城新材料有限公司 | A kind of recovery method as resource of low cost ferric phosphate nitrogen-containing wastewater |
| CN109609760A (en) * | 2018-10-22 | 2019-04-12 | 天齐锂业（江苏）有限公司 | The method of comprehensive utilization of water in a kind of recycling of ferric phosphate lithium cell |
| CN109368612B (en) * | 2018-11-30 | 2022-01-11 | 乳源东阳光磁性材料有限公司 | Method for preparing battery-grade iron phosphate by using iron phosphate production wastewater and iron phosphate prepared by method |
| CN112225380B (en) * | 2020-10-19 | 2022-11-29 | 南通醋酸纤维有限公司 | Resource intensive phosphorus-containing wastewater treatment method |
| CN112759113A (en) * | 2020-12-14 | 2021-05-07 | 广西大学 | Zero discharge of iron phosphate production wastewater and recovery method of phosphate radical and sulfate radical |
| CN113104827B (en) * | 2021-04-25 | 2022-04-29 | 湖北云翔聚能新能源科技有限公司 | Method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution |
| CN113307243B (en) * | 2021-07-08 | 2023-01-24 | 河南佰利新能源材料有限公司 | Method for preparing iron phosphate by recycling mother liquor |
| CN115490219B (en) * | 2022-09-02 | 2024-03-12 | 广东邦普循环科技有限公司 | Ferric phosphate and synthesis process, system and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007049757A1 (en) * | 2007-10-16 | 2009-04-23 | Chemische Fabrik Budenheim Kg | Iron (III) orthophosphate for Li-ion batteries |
| CN101837964A (en) * | 2010-04-29 | 2010-09-22 | 合肥国轩高科动力能源有限公司 | Preparation method of ammonium dihydrogen phosphate by utilizing ammonia generated when producing lithium iron phosphate |
| CN104724688A (en) * | 2015-03-17 | 2015-06-24 | 防城港博森化工有限公司 | Method for preparing low-polymerization-degree water-soluble ammonium polyphosphate from ammonium phosphate |
| CN104944400B (en) * | 2015-07-20 | 2016-09-14 | 河北工业大学 | The technique that Hydrolyze method prepares iron phosphate |
-
2017
- 2017-09-21 CN CN201710856857.7A patent/CN107445139B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107445139A (en) | 2017-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107445139B (en) | The circulation utilization method of mother liquor in a kind of ferric phosphate production process | |
| CN110482512A (en) | A kind of preparation method of battery-grade iron phosphate | |
| CN113104827B (en) | Method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution | |
| CN109250856A (en) | It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource | |
| RU2010143128A (en) | METHOD FOR PRODUCING VANADIUM OXIDE USING ION EXCHANGE FOR CARRYING OUT WASTE WATER CIRCULATION | |
| CN104628206A (en) | Recycling technique of lithium iron phosphate production wastewater | |
| CN113307243B (en) | Method for preparing iron phosphate by recycling mother liquor | |
| CN103011272A (en) | Method for concentrating and purifying titanium dioxide waste acid by using complex acid | |
| CN110540185A (en) | synthesis process of battery-grade iron phosphate | |
| CN113354177B (en) | System and method for recycling iron phosphate ammonia nitrogen-containing wastewater | |
| CN114538404B (en) | Method for preparing lithium iron phosphate from titanium white byproduct ferrous sulfate | |
| CN105967161A (en) | Method for continuously preparing low-cost battery grade ferric phosphate by utilizing iron filings | |
| CN102897803B (en) | Method for recycling mother solution generated in lithium iron phosphate preparation based on liquid phase method | |
| CN103482667B (en) | Quick and efficient purifying method for phosphogypsum | |
| CN103193277A (en) | Method for preparing iron oxide red pigment through copperas | |
| CN109052358A (en) | A kind of preparation method of mesopore-macropore ferric phosphate | |
| CN108751234A (en) | A kind of method of purification of lithium fluoride | |
| CN107416863A (en) | The method that the waste water of ferric phosphate production prepares technical grade ammonium salt | |
| CN103691283A (en) | Method for fixing carbon dioxide in industrial smoke | |
| CN110980679A (en) | Preparation method of spheroidal low-sulfur iron phosphate | |
| CN106276989A (en) | The method that magnesium prepares magnesium hydroxide is reclaimed from cobalt nickel industry is containing cobalt magnesium solution | |
| CN102935327B (en) | Method for removing sulfur dioxide in tail gas from industrial kiln and method for comprehensively utilizing tail gas from industrial kiln | |
| CN108773847A (en) | A method of the waste and old phosphoric acid vanadium lithium of recycling | |
| CN104211106A (en) | Preparation method of rare earth carbonate free of generation of ammonia-nitrogen wastewater | |
| CN107827163A (en) | A kind of preparation method of the amorphous FeOOH desulfurizer of normal temperature high-sulfur accommodation high-strength |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |