CN108313996A - The method for producing battery-grade anhydrous iron phosphate using pyrite cinder - Google Patents
The method for producing battery-grade anhydrous iron phosphate using pyrite cinder Download PDFInfo
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- CN108313996A CN108313996A CN201810268409.XA CN201810268409A CN108313996A CN 108313996 A CN108313996 A CN 108313996A CN 201810268409 A CN201810268409 A CN 201810268409A CN 108313996 A CN108313996 A CN 108313996A
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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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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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
- C01B25/18—Phosphoric acid
- C01B25/20—Preparation from elemental phosphorus or phosphoric anhydride
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/012—Preparation of hydrogen chloride from the elements
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/004—Systems for reclaiming waste heat
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
A method of battery-grade anhydrous iron phosphate being produced using pyrite cinder, is included the following steps：The washings containing hydrochloric acid are sent into electrolytic cell during ferric phosphate is produced, and obtain chlorine；Chlorine is passed through in yellow phosphorus water, is absorbed by yellow phosphorus water, the mixture of phosphoric acid and hydrochloric acid is obtained；The mixture of phosphoric acid and hydrochloric acid is reacted with pyrite cinder, obtains crude product ferric phosphate；In the present invention, after hydrochloric acid in once washing water is by cell reaction, chlorion generates chlorine, chlorine reacts the mixture for generating phosphoric acid and hydrochloric acid with yellow phosphorus water, the mixture of phosphoric acid and hydrochloric acid generates crude product ferric phosphate with pyrite cinder again, to which pyrite cinder be turned waste into wealth, and avoid the exhaust emission environment of chlorion, it is cationic then combined with hydroxyl to be formed precipitation discharge, avoid being continuously increased for cation concn, once washing water by electrolysis processing is recycled, realize the zero-emission of washings, hydrochloric acid in technical process is recycled simultaneously, realize the zero-emission of chlorion.
Description
Technical field
The present invention relates to ferric phosphate preparing technical fields, more particularly to a kind of to produce battery-grade anhydrous phosphorus using pyrite cinder
The method of sour iron.
Background technology
Ferric phosphate can be used as preparing the source of iron of lithium ion battery anode material lithium iron phosphate, but its cost is higher, only phosphoric acid
Iron just accounts for nearly the half of cost of material, it is necessary to the cost of ferric phosphate be greatly lowered, meet the market demand with high performance-price ratio.Sulphur
Sour slag is that pyrite burning extracts the residue being discharged after sulphur.Iron is in slag mainly using ingredient.Currently, pyrite cinder
Comprehensively utilize it is unsatisfactory, it is most of to be handled using landfill other than small part is used as ironmaking and construction material, cause resource
Waste, environment pollution.And using pyrite cinder as the raw material for preparing ferric phosphate, it has no and has been reported that.Ferric phosphate production process
In need to wash it, the hydrochloric acid containing low concentration and some chlorates in washings, if do not handled, washings cannot follow
Ring uses, since hydrochloric acid, chlorination salinity are low, it is difficult to using conventional method processing, such as use neutralization displacement method, that is, use big
It measures lime and neutralization reaction occurs with waste hydrochloric acid.Hydrochloric acid in waste water is handled using this method, processing cost is high, and recovery value is very
It is low, a large amount of waste water are also will produce, environment is polluted, direct emission not only results in waste of resources, and certain shadow can be also caused to environment
It rings, especially chlorion is especially prominent to the pollution of environment, and ferric phosphate contains a certain amount of free water and the crystallization water, common
Processing method is first to use expansion drying, and then electricity consumption baking oven roasts, and this method speed of production is slow, and it is big to bake power consumption.
Invention content
In view of this, against the above deficiency, it is necessary to propose that a kind of energy prepare ferric phosphate using pyrite cinder, and can be effective
The hydrochloric acid and washings in ferric phosphate washings are recycled, zero release of pollutant, especially chlorion zero-emission, and phosphorus are met
Sour iron roasts energy saving, the quick method for producing battery-grade anhydrous iron phosphate using pyrite cinder.
A method of battery-grade anhydrous iron phosphate being produced using pyrite cinder, is included the following steps：Step 1：By sulfuric acid
Slag and the second phosphatase reaction, to obtain crude product ferric phosphate, wherein the mass percentage concentration of the second phosphoric acid is 20~80%；
Step 2：By the second dissolving with hydrochloric acid of crude product ferric phosphate, and clear liquid and filter residue is obtained by filtration, wherein the quality of the second hydrochloric acid
Percentage concentration is 20~30%；
Step 3：The clear liquid is distilled, to obtain gaseous hydrogen chloride and ferric phosphate crystallized product；
Step 4：Gaseous hydrogen chloride is condensed, the 4th hydrochloric acid is obtained, the 4th hydrochloric acid rectifying is obtained into the second hydrochloric acid, by this step
In obtained the second hydrochloric acid be back in step 2, to dissolve crude product ferric phosphate, wherein the mass percentage concentration of the 4th color
To be less than 5%；
Step 5：Ferric phosphate crystallized product is washed with second wash water, obtain purification of phosphoric acid iron and contains once washing water,
Wherein, the once washing water be containing mass percentage concentration be 1~5% the first hydrochloric acid washings, in the once washing water
Also contain chlorate, the corresponding hydroxide of cation of the chlorate is not soluble in water, and second wash water is removal chloride
Once washing water；
Step 6：Once washing water is sent into electrolysis unit electrolysis, to obtain chlorine, hydrogen, hydroxyl sediment, secondary washing
Water, hydrogen is discharged from hydrogen discharge mouth, and hydroxyl sediment is discharged from electrolytic cell, second wash water is back to step
Five, to wash ferric phosphate crystallized product, second wash water is changed into once washing water again；
Step 7：The chlorine is passed through in yellow phosphorus water, and is absorbed by yellow phosphorus water, to obtain the mixed of the first phosphoric acid and third hydrochloric acid
Close object；
Step 8：The mixture of first phosphoric acid and third hydrochloric acid is back in step 1, to be reacted with pyrite cinder；
Step 9：The purification of phosphoric acid iron obtained in step 5 is sent into the roasting of drying and calcining device, obtains anhydrous iron phosphate, it is described
Drying and calcining device include the drying and calcining device include direct combustion hotblast stove, dynamic calcining tower, first discharging cyclone,
Transfer wind turbine, Rotatingandflashstreamingdrier, the first reel, the second discharging cyclone, the second reel, bag filter, air-introduced machine,
The air outlet of the direct combustion hotblast stove is connected to the air inlet of dynamic calcining tower, to provide thermal energy for dynamic calcining tower, dynamic
The discharge port for calcining top of tower is connected to the feed inlet of the first discharging cyclone, and the bottom of the first discharging cyclone is set
There is anhydrous iron phosphate outlet, the air outlet at the top of the first discharging cyclone is connected to the air inlet of transfer wind turbine, described
The air outlet of transfer wind turbine is connected to the air inlet of Rotatingandflashstreamingdrier, so that the high-temperature gas warp flowed out from dynamic calcining tower
It crosses transfer wind turbine and is sent into Rotatingandflashstreamingdrier, to provide thermal energy for Rotatingandflashstreamingdrier, the Rotatingandflashstreamingdrier
Feed inlet is connect with the first reel, purification of phosphoric acid iron to be dried is sent into Rotatingandflashstreamingdrier, institute by the first reel
It states the discharge port at the top of Rotatingandflashstreamingdrier to be connected to the feed inlet of the second discharging cyclone, the first discharging rotation
The bottom of wind apparatus is exported equipped with phosphate dihydrate iron, phosphate dihydrate iron outlet by the second reel and dynamic calcining tower into
Material mouth be connected to, by phosphate dihydrate iron feeding dynamic calcining tower roast, it is described second discharging cyclone air outlet with
The entrance of bag filter is connected to, and the outlet of the bag filter is connected to air-introduced machine.
In the present invention, after hydrochloric acid, phosphorus chloride, magnesium chloride, calcium chloride in once washing water are by cell reaction, chlorion
Chlorine is generated, chlorine reacts the mixture of generation the first phosphoric acid and third hydrochloric acid with yellow phosphorus water, the first phosphoric acid and third hydrochloric acid
Mixture generates crude product ferric phosphate with pyrite cinder again, to which pyrite cinder be turned waste into wealth by recycling for chlorion,
And avoid the exhaust emission environment of chlorion, it is cationic then combined with hydroxyl to be formed precipitation discharge, avoid cation concn
Be continuously increased so that by electrolysis processing once washing water can recycle, realize the zero-emission of washings, technique
Hydrochloric acid in the process is recycled by dissolving, filtering, distillation, condensation, rectification process, realizes the zero-emission of chlorion
It puts, using drying and calcining device dynamic calcining, is heated, realized for Rotatingandflashstreamingdrier using the gas of dynamic calcining tower discharge
Heat recovery, thus it is more energy saving；Ferric phosphate by Rotatingandflashstreamingdrier drying returns to the roasting of dynamic calcining tower,
It ensure that quick production.
Description of the drawings
Fig. 1 is the flow chart for the method that battery-grade anhydrous iron phosphate is produced using pyrite cinder.
Fig. 2 is the structural schematic diagram of the evaporative condenser.
Fig. 3 is the structural schematic diagram of the boiling wall.
Fig. 4 is the structural schematic diagram in condensation pipe main view direction.
Fig. 5 is the structural schematic diagram of the right apparent direction of the condensation pipe.
Fig. 6 is the structural schematic diagram of the drying and calcining device overlook direction.
Fig. 7 is the structural schematic diagram in the directions drying and calcining device A.
Fig. 8 is the structural schematic diagram in the directions drying and calcining device B.
In figure：Evaporation boiler 10, water inlet line 11, the first solenoid valve 111, outlet conduit 12, second solenoid valve 121, condensation
Pipeline 13, condensation part 131, baffle plate 1311, fluid level controller 14, boiling wall 15, heating furnace 20, combustion chamber 21, Hydrogen Line
22, drainage pipeline 23, combustion gas duct 24, drying and calcining device 30, direct combustion hotblast stove 31, dynamic calcining tower 32, first
Discharge cyclone 33, transfer wind turbine 34, Rotatingandflashstreamingdrier 35, the first reel 36, second discharging cyclone 37, second
Reel 38, bag filter 39, air-introduced machine 310.
Specific implementation mode
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be apparent that, drawings in the following description are some embodiments of the invention, common for this field
For technical staff, without creative efforts, other drawings may also be obtained based on these drawings.
Referring to Fig. 1, an embodiment of the present invention provides a kind of method for producing battery-grade anhydrous iron phosphate using pyrite cinder,
Include the following steps：
Step S300：By pyrite cinder and the second phosphatase reaction, to obtain crude product ferric phosphate, wherein the quality percentage of the second phosphoric acid
A concentration of 20~80%；
Step S301：By the second dissolving with hydrochloric acid of crude product ferric phosphate, and clear liquid and filter residue is obtained by filtration, wherein the matter of the second hydrochloric acid
It is 20~30% to measure percentage concentration；
Step S302：The clear liquid is distilled, to obtain gaseous hydrogen chloride and ferric phosphate crystallized product；
Step S303：Gaseous hydrogen chloride is condensed, the 4th hydrochloric acid is obtained, the 4th hydrochloric acid rectifying is obtained into the second hydrochloric acid, this is walked
The second hydrochloric acid obtained in rapid is back in step S301, to dissolve crude product ferric phosphate, wherein the quality percentage of the 4th color
It is a concentration of to be less than 5%；
Step S304：Ferric phosphate crystallized product is washed with second wash water, purification of phosphoric acid iron is obtained and contains once washing
Water, wherein the once washing water be containing mass percentage concentration be 1~5% the first hydrochloric acid washings, the once washing
Also contain chlorate in water, the corresponding hydroxide of cation of the chlorate is not soluble in water, and second wash water is removal chlorination
The once washing water of object；
Step S305：Once washing water is sent into electrolysis unit electrolysis, to obtain chlorine, hydrogen, hydroxyl sediment, secondary wash
Water is washed, hydrogen is discharged from hydrogen discharge mouth, hydroxyl sediment is discharged from electrolytic cell, second wash water is back to step
S304, to wash ferric phosphate crystallized product, second wash water is changed into once washing water again, wherein second wash water is to go
Except the once washing water of chloride；
Step S306：The chlorine is passed through in yellow phosphorus water, and is absorbed by yellow phosphorus water, to obtain the first phosphoric acid and third hydrochloric acid
Mixture；
Step S307：The mixture of first phosphoric acid and third hydrochloric acid is back in step S300, to be reacted with pyrite cinder；
Step S308：The purification of phosphoric acid iron obtained in step S304 is sent into drying and calcining device 30 to roast, obtains anhydrous phosphoric acid
Iron, drying and calcining device 30 include direct combustion hotblast stove 31, the discharging of dynamic calcining tower 32, first cyclone 33, transfer wind turbine
34, Rotatingandflashstreamingdrier 35, the first reel 36, second discharging cyclone 37, the second reel 38, bag filter 39, draw
The air outlet of wind turbine 310, direct combustion hotblast stove 31 is connected to the air inlet of dynamic calcining tower 32, to be provided for dynamic calcining tower 32
Thermal energy, the discharge port at 32 top of dynamic calcining tower are connected to the feed inlet of the first discharging cyclone 33, the first discharging bookbinding method
It sets 33 bottom to export equipped with anhydrous iron phosphate, the air inlet of the air outlet and transfer wind turbine 34 at 33 top of the first discharging cyclone
Mouth connection, the air outlet of transfer wind turbine 34 are connected to the air inlet of Rotatingandflashstreamingdrier 35, so as to be flowed from dynamic calcining tower 32
The high-temperature gas gone out is sent into Rotatingandflashstreamingdrier 35 by transfer wind turbine 34, to provide thermal energy for Rotatingandflashstreamingdrier 35,
The feed inlet of Rotatingandflashstreamingdrier 35 is connect with the first reel 36, with by the first reel 36 by purification of phosphoric acid iron to be dried
It is sent into Rotatingandflashstreamingdrier 35, the feed inlet of the discharge port at 35 top of Rotatingandflashstreamingdrier and the second discharging cyclone 37
The bottom of connection, the first discharging cyclone 33 is exported equipped with phosphate dihydrate iron, and the outlet of phosphate dihydrate iron passes through the second reel 38
It is connected to the feed inlet of dynamic calcining tower 32, phosphate dihydrate iron, which is sent into dynamic calcining tower 32, to be roasted, the second discharging rotation
The air outlet of wind apparatus 37 is connected to the entrance of bag filter 39, and the outlet of bag filter 39 is connected to air-introduced machine 310；
The detailed process roasted to purification of phosphoric acid iron by above-mentioned drying and calcining device 30 is：Purification of phosphoric acid Tie Tong is crossed
One reel 36 is sent into after Rotatingandflashstreamingdrier 35 dries, and obtains phosphate dihydrate iron, and phosphate dihydrate iron is from the second discharging bookbinding method
37 outflows are set, then dynamic calcining tower 32 is sent by the second reel 38 and is roasted, then flows out, obtains from the first discharging cyclone 33
Anhydrous iron phosphate.
In wherein Fig. 1, one finger chlorine of reaction is reacted with yellow phosphorus water, and two finger phosphoric acid of reaction is reacted with pyrite cinder.
The purification of phosphoric acid iron obtained in above-mentioned steps S304, using 30 dynamic calcining of drying and calcining device, using dynamically forging
It burns the gas that tower 32 is discharged to heat for Rotatingandflashstreamingdrier 35, realizes heat recovery, therefore more energy saving；Through overwinding
The ferric phosphate for turning the drying of flash dryer 35 returns to 32 roasting of dynamic calcining tower, ensure that quick production.
In the present invention, after hydrochloric acid, phosphorus chloride, magnesium chloride, calcium chloride in once washing water are by cell reaction, chlorion
Chlorine is generated, chlorine reacts the mixture of generation the first phosphoric acid and third hydrochloric acid with yellow phosphorus water, the first phosphoric acid and third hydrochloric acid
Mixture generates crude product ferric phosphate with pyrite cinder again, to which pyrite cinder be turned waste into wealth by recycling for chlorion,
And avoid the exhaust emission environment of chlorion, it is cationic then combined with hydroxyl to be formed precipitation discharge, avoid cation concn
Be continuously increased so that by electrolysis processing once washing water can recycle, realize the zero-emission of washings, technique
Hydrochloric acid in the process is recycled by dissolving, filtering, distillation, condensation, rectification process, realizes the zero-emission of chlorion
It puts, using 30 dynamic calcining of drying and calcining device, is added for Rotatingandflashstreamingdrier 35 using the gas that dynamic calcining tower 32 is discharged
Heat realizes heat recovery, therefore more energy saving；The ferric phosphate dried by Rotatingandflashstreamingdrier 35 returns to dynamic and forges
It burns tower 32 to roast, ensure that quick production.
Referring to Fig. 1, further, the once washing water in step 304 passes through pretreated step before being electrolysed in step 305
Suddenly, which is that once washing water is passed through evaporative condenser, the washings for being 1~5% by mass percentage concentration
Concentration, the evaporative condenser use the hydrogen heating discharged in step 305.
In present embodiment, the hydrogen that cell reaction is generated is used for the evaporation and concentration of once washing, is once washed with improving
Water electrolysis efficiency is washed, electrolysis energy consumption is reduced, while both having avoided the exhaust emission environment of hydrogen, in turn avoids energy waste.
Referring to Fig. 2, further, evaporative condenser includes evaporation boiler 10, heating furnace 20, and hydrogen is equipped on heating furnace 20
Pipeline 22, drainage pipeline 23, combustion gas duct 24 are equipped with water inlet line 11, outlet conduit 12, condensation on evaporation boiler 10
Pipeline 13, fluid level controller 14, evaporation boiler 10 pass through the round hole of 20 roof of heating furnace, and are nested into internally heated oven 20, evaporate
The round hole internal ring wall of pot 10 top external annulus and 20 roof of heating furnace is fixed, is tightly connected, one end of Hydrogen Line 22 with add
21 bottom of combustion chamber of hot stove 20 is connected to, and the other end of Hydrogen Line 22 is connected to the hydrogen discharge mouth of electrolysis unit, heating furnace
20 21 bottom of combustion chamber is communicated with drainage pipeline 23, the water generated after combustion of hydrogen is discharged, the combustion chamber of heating furnace 20
21 bottoms are communicated with combustion gas duct 24, and air is passed through in the combustion chamber 21 of heating furnace 20, and evaporative condenser top connects
It is connected to water inlet line 11, once washing water to be pre-treated is passed through evaporative condenser, is equipped on water inlet line 11
One solenoid valve 111, evaporative condenser lower part are connected with outlet conduit 12, and the once washing after being concentrated by evaporation is passed through electrolysis
Slot, is equipped with second solenoid valve 121 on outlet conduit 12, and after the water evaporation in above-mentioned evaporative condenser, water vapour is evaporating
Condenser overhead is delivered to use from the water outlet at the top of evaporative condenser at condensed water, the condensed water by condensation pipe 13
Point is equipped with fluid level controller 14, fluid level controller 14 and control mould to wash ferric phosphate crystallized product in evaporative condenser
Block is electrically connected, and control module is electrically connected with the first solenoid valve 111, second solenoid valve 121, and the water level in evaporative condenser exists
When low water level, fluid level controller 14 sends out the low signal of water level to control module, and controller module controls the first solenoid valve 111 and beats
It opens, the closing of second solenoid valve 121, for the water level in evaporative condenser in high water level, fluid level controller 14 sends out the high letter of water level
Number give control module, control module control the first solenoid valve 111 close, second solenoid valve 121 open.
In the present embodiment, the first solenoid valve 111 is controlled by fluid level controller 14 and is closed, second solenoid valve 121 is intermittently opened
Or close, to control the liquid level of once washing water in evaporative condenser, to which indirect control is washed by pretreated first
The mass percentage concentration of the middle hydrochloric acid of water, to provide the hydrochloric acid required containing specified mass percentage concentration for electrolysis unit interval
Once washing water.
Referring to Fig. 2 and Fig. 3, further, in evaporative condenser has and contacted with the raw water in it, and to heat raw water
Boil wall 15, and the side that boiling wall 15 is contacted with raw water is densely covered with tiny protrusion, and the free end of protrusion is arranged to tip.
In the present embodiment, part that evaporative condenser is contacted with water, and heated to water is arranged to the wall 15 that boils, and one
Aspect increases disengagement area by densely covered tiny protrusion, is on the other hand gas by the way that the free end of protrusion is arranged to tip
Bubble production provides growth cores, to promote the evaporation of water.
Referring to Fig. 2, Fig. 4, Fig. 5, further, 13 section of condensation pipe is rectangular, square along its length in condensation pipe 13
Multiple condensation parts 131 are inserted to uniform intervals, condensation part 131 includes two baffle plates 1311, and two baffle plates 1311 are reversed
It is obliquely installed, each baffle plate 1311 is trapezoidal, and vertical with exhaust duct inside side walls.
Baffle plate 1311 adjusts the mobility status of vapor in condensation pipe 13, after vapor encounters baffle plate 1311, one
Small part condensed water flows downward along baffle plate 1311, while multiple baffle plates 1311 increase the heat exchange area of vapor,
Accelerate the cohesion of vapor, after the condensation film to certain thickness on baffle plate 1311, edge under the action of gravity and air-flow
It baffle plate 1311 and is gathered in 13 bottom of condensation pipe, point of use is flow to further along 13 bottom of condensation pipe, to wash phosphoric acid
Iron crystallized product effectively accelerates vapor condensation effect, which neither additionally increases device structure, and can be fully
Using the space in the pipeline of existing device, and acceleration vapor condensation effect, simple structure, practicality are reached.
Further, the electrolytic process of once washing water is in step S305, will pass through by pretreated once washing water
Diaphragm or cationic membrane electrolytic cell are that anode obtains chlorine and hydrogen using copper mesh as cathode, titanium alloy, and electrolysis uses continuous multi-stage
Mode, i.e., row supplements new once washing water and carries out two level electrolysis the once washing water after level-one electrolysis again, after two level electrolysis
Once washing water be supplemented new once washing water and carry out three-level electrolysis, and so on.
It in present embodiment, uses copper mesh for cathode, chlorion can be effectively reduced in diffusion length in the electrolytic solution, subtracted
Small electrolysis energy consumption is more suitable for the preparing chlorine by electrolysis gas of low concentration of salt aqueous acid.
The steps in the embodiment of the present invention can be sequentially adjusted, merged and deleted according to actual needs.
Module or unit in device of the embodiment of the present invention can be combined, divided and deleted according to actual needs.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, those skilled in the art can understand all or part of the processes for realizing the above embodiment, and is wanted according to right of the present invention
Equivalent variations made by asking, still belong to the scope covered by the invention.
Claims (6)
1. a kind of method for producing battery-grade anhydrous iron phosphate using pyrite cinder, it is characterised in that include the following steps：
Step 1：By pyrite cinder and the second phosphatase reaction, to obtain crude product ferric phosphate, wherein the quality percentage of the second phosphoric acid is dense
Degree is 20~80%；
Step 2：By the second dissolving with hydrochloric acid of crude product ferric phosphate, and clear liquid and filter residue is obtained by filtration, wherein the quality of the second hydrochloric acid
Percentage concentration is 20~30%；
Step 3：The clear liquid is distilled, to obtain gaseous hydrogen chloride and ferric phosphate crystallized product；
Step 4：Gaseous hydrogen chloride is condensed, the 4th hydrochloric acid is obtained, the 4th hydrochloric acid rectifying is obtained into the second hydrochloric acid, by this step
In obtained the second hydrochloric acid be back in step 2, to dissolve crude product ferric phosphate, wherein the mass percentage concentration of the 4th color
To be less than 5%；
Step 5：Ferric phosphate crystallized product is washed with second wash water, obtain purification of phosphoric acid iron and contains once washing water,
Wherein, the once washing water be containing mass percentage concentration be 1~5% the first hydrochloric acid washings, in the once washing water
Also contain chlorate, the corresponding hydroxide of cation of the chlorate is not soluble in water, and second wash water is removal chloride
Once washing water；
Step 6：Once washing water is sent into electrolysis unit electrolysis, to obtain chlorine, hydrogen, hydroxyl sediment, secondary washing
Water, hydrogen is discharged from hydrogen discharge mouth, and hydroxyl sediment is discharged from electrolytic cell, second wash water is back to step
Five, to wash ferric phosphate crystallized product, second wash water is changed into once washing water again；
Step 7：The chlorine is passed through in yellow phosphorus water, and is absorbed by yellow phosphorus water, to obtain the mixed of the first phosphoric acid and third hydrochloric acid
Close object；
Step 8：The mixture of first phosphoric acid and third hydrochloric acid is back in step 1, to be reacted with pyrite cinder；
Step 9：The purification of phosphoric acid iron obtained in step 5 is sent into the roasting of drying and calcining device, obtains anhydrous iron phosphate, it is described
Drying and calcining device include the drying and calcining device include direct combustion hotblast stove, dynamic calcining tower, first discharging cyclone,
Transfer wind turbine, Rotatingandflashstreamingdrier, the first reel, the second discharging cyclone, the second reel, bag filter, air-introduced machine,
The air outlet of the direct combustion hotblast stove is connected to the air inlet of dynamic calcining tower, to provide thermal energy for dynamic calcining tower, dynamic
The discharge port for calcining top of tower is connected to the feed inlet of the first discharging cyclone, and the bottom of the first discharging cyclone is set
There is anhydrous iron phosphate outlet, the air outlet at the top of the first discharging cyclone is connected to the air inlet of transfer wind turbine, described
The air outlet of transfer wind turbine is connected to the air inlet of Rotatingandflashstreamingdrier, so that the high-temperature gas warp flowed out from dynamic calcining tower
It crosses transfer wind turbine and is sent into Rotatingandflashstreamingdrier, to provide thermal energy for Rotatingandflashstreamingdrier, the Rotatingandflashstreamingdrier
Feed inlet is connect with the first reel, purification of phosphoric acid iron to be dried is sent into Rotatingandflashstreamingdrier, institute by the first reel
It states the discharge port at the top of Rotatingandflashstreamingdrier to be connected to the feed inlet of the second discharging cyclone, the first discharging rotation
The bottom of wind apparatus is exported equipped with phosphate dihydrate iron, phosphate dihydrate iron outlet by the second reel and dynamic calcining tower into
Material mouth be connected to, by phosphate dihydrate iron feeding dynamic calcining tower roast, it is described second discharging cyclone air outlet with
The entrance of bag filter is connected to, and the outlet of the bag filter is connected to air-introduced machine.
2. the method for producing battery-grade anhydrous iron phosphate using pyrite cinder as described in claim 1, it is characterised in that：Step
Once washing water in five passes through pretreated step before being electrolysed in step 6, which is, by once washing
By evaporative condenser, the washings that mass percentage concentration is 1~5% are concentrated, the evaporative condenser uses in step 6
The hydrogen of discharge heats.
3. the method for producing battery-grade anhydrous iron phosphate using pyrite cinder as claimed in claim 2, it is characterised in that：It is described
Evaporative condenser includes evaporation boiler, heating furnace, and Hydrogen Line, drainage pipeline, combustion gas duct are equipped on heating furnace,
Water inlet line, outlet conduit, condensation pipe, fluid level controller are installed, the evaporation boiler passes through heating furnace roof on evaporation boiler
Round hole, and be nested into internally heated oven, the round hole internal ring wall of evaporation boiler top external annulus and heating furnace roof fixes,
It is tightly connected, one end of the Hydrogen Line is connected to the bottom of combustion chamber of heating furnace, the other end and the electricity of the Hydrogen Line
The hydrogen discharge mouth connection of device is solved, the bottom of combustion chamber of the heating furnace is communicated with drainage pipeline, will be raw after combustion of hydrogen
At water discharge, the bottom of combustion chamber of the heating furnace is communicated with combustion gas duct, air is passed through to the burning of heating furnace
Interior, the evaporative condenser top are connected with water inlet line, and once washing water to be pre-treated is passed through evaporative condenser,
First solenoid valve is installed on water inlet line, the evaporative condenser lower part is connected with outlet conduit, after being concentrated by evaporation
Once washing be passed through electrolytic cell, second solenoid valve is installed on outlet conduit, after the water evaporation in above-mentioned evaporative condenser,
For water vapour at condensed water at the top of evaporative condenser, the condensed water is defeated by condensation pipe from the water outlet at the top of evaporative condenser
It send to point of use, to wash ferric phosphate crystallized product, fluid level controller, the liquid level control is installed in the evaporative condenser
Device processed is electrically connected with control module, and the control module is electrically connected with the first solenoid valve, second solenoid valve, evaporative condenser
For interior water level in low water level, fluid level controller sends out the low signal of water level to control module, the first electricity of controller module control
Magnet valve is opened, second solenoid valve is closed, and for the water level in evaporative condenser in high water level, fluid level controller sends out the high letter of water level
Number give control module, control module control the first solenoid valve close, second solenoid valve open.
4. the method for producing battery-grade anhydrous iron phosphate using pyrite cinder as claimed in claim 3, it is characterised in that：It is described
Have in evaporative condenser and contacted with the raw water in it, and to heat the boiling wall of raw water, the boiling wall is contacted with raw water
Side be densely covered with tiny protrusion, the free end of the protrusion is arranged to tip.
5. the method for producing battery-grade anhydrous iron phosphate using pyrite cinder as claimed in claim 3, it is characterised in that：It is described
Condensation pipe section is rectangular, and uniform intervals have inserted multiple condensation parts, the condensation along its length in condensation pipe
Portion includes two baffle plates, and the setting of two baffle plate reversed dips, each baffle plate is trapezoidal, and with side on the inside of exhaust duct
Wall is vertical.
6. the method for producing battery-grade anhydrous iron phosphate using pyrite cinder as described in claim 1, it is characterised in that：Step
The electrolytic process of once washing water is in six, will pass through pretreated once washing water by diaphragm or cationic membrane electrolytic cell,
It is that anode obtains chlorine and hydrogen using copper mesh as cathode, titanium alloy, is electrolysed by the way of continuous multi-stage, i.e., after level-one electrolysis
Row supplements new once washing water progress two level electrolysis to once washing water again, and the once washing water after two level electrolysis is supplemented new
Once washing water carries out three-level electrolysis, and so on.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109650365A (en) * | 2019-03-06 | 2019-04-19 | 深圳海纳百川科技有限公司 | A kind of the drying and sintering technique and its device of ferric phosphate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092698A (en) * | 2010-12-03 | 2011-06-15 | 何侠 | Method for preparing sulfuric-acid burned slag into phosphate with chemical method |
| CN102491302A (en) * | 2011-12-15 | 2012-06-13 | 湖北万润新能源科技发展有限公司 | Battery-grade anhydrous iron phosphate and preparation method thereof |
| WO2014178788A1 (en) * | 2013-05-02 | 2014-11-06 | Easymining Sweden Ab | Production of phosphate compounds from materials containing phosphorus and at least one of iron and aluminium |
| CN105600764A (en) * | 2014-09-17 | 2016-05-25 | 常德云港生物科技有限公司 | Method for producing phosphate by using sulfuric acid sintering residue |
| CN107611433A (en) * | 2017-09-19 | 2018-01-19 | 江苏荣信环保科技有限公司 | A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid |
-
2018
- 2018-03-29 CN CN201810268409.XA patent/CN108313996B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092698A (en) * | 2010-12-03 | 2011-06-15 | 何侠 | Method for preparing sulfuric-acid burned slag into phosphate with chemical method |
| CN102491302A (en) * | 2011-12-15 | 2012-06-13 | 湖北万润新能源科技发展有限公司 | Battery-grade anhydrous iron phosphate and preparation method thereof |
| WO2014178788A1 (en) * | 2013-05-02 | 2014-11-06 | Easymining Sweden Ab | Production of phosphate compounds from materials containing phosphorus and at least one of iron and aluminium |
| CN105600764A (en) * | 2014-09-17 | 2016-05-25 | 常德云港生物科技有限公司 | Method for producing phosphate by using sulfuric acid sintering residue |
| CN107611433A (en) * | 2017-09-19 | 2018-01-19 | 江苏荣信环保科技有限公司 | A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109650365A (en) * | 2019-03-06 | 2019-04-19 | 深圳海纳百川科技有限公司 | A kind of the drying and sintering technique and its device of ferric phosphate |
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