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
The method that sour iron roasts energy saving, quick dry process low-grade phosphate ore ferric phosphate made of stones.
A kind of method of dry process low-grade phosphate ore ferric phosphate made of stones, includes the following steps:
Step 1:Rock phosphate powder is broken to 80~90 mesh, obtains ground phosphate rock, the wherein grade of rock phosphate in powder is 10~28%;
Step 2:By ground phosphate rock and sulfuric acid reaction, slurry phosphoric acid and hydrogen fluoride are obtained, the wherein mass percentage concentration of sulfuric acid is 10
~80%;
Step 3:Above-mentioned hydrogen fluoride is reacted with caustic soda, sodium fluoride is made, above-mentioned slurry phosphoric acid is calcined, to obtain gaseous state phosphorus
Acid and calcium sulfate so that gaseous state phosphoric acid and calcium sulfate separation;
Step 4:It collects above-mentioned gaseous state phosphoric acid and obtains the second phosphoric acid;
Step 5: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 6: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 7:The clear liquid is distilled, to obtain gaseous hydrogen chloride and ferric phosphate crystallized product;
Step 8: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 6, to dissolve crude product ferric phosphate, wherein the mass percentage concentration of the 4th color
To be less than 5%;
Step 9: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 10: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
Nine, to wash ferric phosphate crystallized product, second wash water is changed into once washing water again;
Step 11: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 12:The mixture of first phosphoric acid and third hydrochloric acid is back in step 5, to be reacted with pyrite cinder;
Step 13:The purification of phosphoric acid iron obtained in step 9 is sent into the roasting of drying and calcining device, obtains anhydrous iron phosphate, institute
It includes direct combustion hotblast stove, dynamic calcining tower, the first discharging cyclone, transfer wind turbine, rotary flash distillation to state drying and calcining device
Drying machine, the first reel, the second discharging cyclone, the second reel, bag filter, air-introduced machine, the direct combustion hotblast stove
Air outlet be connected to the air inlet of dynamic calcining tower, to provide thermal energy, the discharging of dynamic calcining top of tower for dynamic calcining tower
Mouth is connected to the feed inlet of the first discharging cyclone, and the bottom of the first discharging cyclone goes out equipped with anhydrous iron phosphate
Mouthful, the air outlet at the top of the first discharging cyclone is connected to the air inlet of transfer wind turbine, the outlet air of the transfer wind turbine
Mouth is connected to the air inlet of Rotatingandflashstreamingdrier, so that the high-temperature gas flowed out from dynamic calcining tower is sent by transfer wind turbine
Rotatingandflashstreamingdrier, to provide thermal energy for Rotatingandflashstreamingdrier, the feed inlet of the Rotatingandflashstreamingdrier and first twist
Wheel connection, purification of phosphoric acid iron to be dried is sent into Rotatingandflashstreamingdrier, the rotary flashing drying by the first reel
Discharge port at the top of machine is connected to the feed inlet of the second discharging cyclone, and the bottom of the first discharging cyclone is set
There are the outlet of phosphate dihydrate iron, the phosphate dihydrate iron outlet to be connected to the feed inlet of dynamic calcining tower by the second reel, it will
Phosphate dihydrate iron is sent into dynamic calcining tower and is roasted, the second discharging air outlet of cyclone and entering for bag filter
Mouth connection, 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.
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 methods of dry process low-grade phosphate ore ferric phosphate made of stones, including
Following steps:
Step S300:Rock phosphate powder is broken to 80~90 mesh, obtains ground phosphate rock, the wherein grade of rock phosphate in powder is 10~28%;
Step S301:By ground phosphate rock and sulfuric acid reaction, slurry phosphoric acid and hydrogen fluoride are obtained, the mass percentage concentration of wherein sulfuric acid is
10~80%;
Step S302:Above-mentioned hydrogen fluoride is reacted with caustic soda, sodium fluoride is made, above-mentioned slurry phosphoric acid is calcined, preferably 850~
Calcined within the temperature range of 950 DEG C, to obtain gaseous state phosphoric acid and calcium sulfate so that gaseous state phosphoric acid and calcium sulfate separation;
Step S303:It collects above-mentioned gaseous state phosphoric acid and obtains the second phosphoric acid;
Step S304: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 S305: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 S306:The clear liquid is distilled, to obtain gaseous hydrogen chloride and ferric phosphate crystallized product;
Step S307: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 S305, 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 S308: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 S309: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
S308, 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 S310: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 S311:The mixture of first phosphoric acid and third hydrochloric acid is back in step S304, to be reacted with pyrite cinder;
Step S312:The purification of phosphoric acid iron obtained in step S308 is sent into the roasting of drying and calcining device, obtains anhydrous iron phosphate,
Drying and calcining device 30 include 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, the second reel 38, bag filter 39, air-introduced machine
310, the air outlet of direct combustion hotblast stove 31 is connected to the air inlet of dynamic calcining tower 32, to provide heat for dynamic calcining tower 32
Can, the discharge port at 32 top of dynamic calcining tower is connected to the feed inlet of the first discharging cyclone 33, the first discharging cyclone
33 bottom is exported 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
Connection, the air outlet of transfer wind turbine 34 are connected to the air inlet of Rotatingandflashstreamingdrier 35, so as to be flowed out from dynamic calcining tower 32
High-temperature gas by transfer wind turbine 34 be sent into Rotatingandflashstreamingdrier 35, to provide thermal energy for Rotatingandflashstreamingdrier 35, rotation
The feed inlet for turning flash dryer 35 is connect with the first reel 36, to be sent purification of phosphoric acid iron to be dried by the first reel 36
Enter Rotatingandflashstreamingdrier 35, the feed inlet company of the discharge port at 35 top of Rotatingandflashstreamingdrier and the second discharging cyclone 37
Logical, the bottom of the first discharging cyclone 33 is equipped with phosphate dihydrate iron and exports, the outlet of phosphate dihydrate iron by the second reel 38 and
The feed inlet of dynamic calcining tower 32 is connected to, and phosphate dihydrate iron, which is sent into dynamic calcining tower 32, to be roasted, the second discharging whirlwind
The air outlet of device 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 reaction two refers to the first phosphoric acid and third hydrochloric acid and sulfuric acid
The reaction of slag, three finger ground phosphate rock of reaction are reacted with sulfuric acid, and four finger hydrogen fluoride of reaction is reacted with caustic soda.
In above-mentioned steps S302, using caustic soda and hydrogen fluoride reaction, fluorination hydrogen contamination environment, the fluorination of generation are both prevented
Sodium can also be sold.
The purification of phosphoric acid iron obtained in above-mentioned steps S308, 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.
Above-mentioned steps S302 can obtain not phosphorous calcium sulfate, and quality fully meets the requirement of manufacture of cement quotient.
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 308 passes through pretreated step before being electrolysed in a step 309
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 309.
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 S309, 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.