CN106430787A - APT (ammonium paratungstate) production wastewater recycling method - Google Patents
APT (ammonium paratungstate) production wastewater recycling method Download PDFInfo
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- CN106430787A CN106430787A CN201610985109.4A CN201610985109A CN106430787A CN 106430787 A CN106430787 A CN 106430787A CN 201610985109 A CN201610985109 A CN 201610985109A CN 106430787 A CN106430787 A CN 106430787A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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Abstract
The invention discloses an APT (ammonium paratungstate) production wastewater recycling method. An APT production line which can realize zero emission of wastewater and is high in water recycling rate can be established, tungsten, molybdenum and other useful metals in a tail liquid can be recycled, loss of tungsten can be avoided, and the added output value can be increased, so that the economic benefit is increased; one part of the discharged tail liquid is recycled to be used for pulping, the other part is evaporated, steam condensate is recycled to be used for preparation of a back washing agent, and thus, zero emission of wastewater is realized. A conventional steam heating manner is changed in a caustification process, a good effect can also be realized through storage tank standing treatment, and the utilization rate of lime can reach 80%, so that steam is saved. Produced APT can meet the notational 0-level standard.
Description
Technical field
A kind of the present invention relates to resource reclaim recycles field, it particularly relates to APT production cycling utilization of wastewater side
Method.
Background technology
In prior art, from sodium tungstate solution, purification and impurity removal produces ammonium paratungstate APT (Ammonium
Paratungstate) commercial run of solution has three kinds, i.e. the chemical method of classics, ion exchange and solvent extraction, wherein
Classical chemical method is due to consuming the low less employing at present of big, yield.Ion exchange respectively has its advantage with solvent extraction
And deficiency, each producer is regarding concrete condition selection.
Ion exchange can remove the anionic impurity such as dephosphorization, arsenic, silicon, work compared with solvent extraction while transition
Skill flow process is short, and operation is relatively simple, but haves the shortcomings that water consumption is big and wastewater discharge is big, in addition, the crystallization of ion exchange
Mother solution directly cannot return main flow and need to set aided process recovery.Solvent-extracted advantage under acid condition is process
Water consumption and wastewater discharge are little, for the area of water limited and draining difficulty favorably.But it is molten under existing acid condition
Agent extraction there is also deficiency, i.e. extraction process and only play transition effect without impurity removal function, and remove impurity still adopts chemical precipitation method, because
This flow process is longer, and has waste residue to produce, though wastewater discharge reduces many than ion exchange, one ton of APT of production is still needed to
About 35 cubic metres of high-concentration salt-containing wastewater of discharge.
Solvent extraction prepares mainly comprising the steps for APT：By caustic soda or soda leaching tungsten mineral material, obtain
Obtain coarse sodium tungstate；By solvent extraction remove impurity and make the transition, obtain pure tungsten acid ammonium solution；Pass through evaporative crystallization again, obtain APT
Product.
The purifying and impurity-removing method for APT being prepared by solvent extraction is extremely difficult to environmental protection zero-emission and water circulation use rate
Standard.At least there is following technical problem in prior art：Waste water discharge opening must be set, and waste water pollution problem cannot thorough root
Remove；Supplies are mostly expendable consumed product, and the leaching agent of leaching process is excessively used, and these supplies are in corresponding work
Or skill step reaction finish after directly outer row need using in corresponding acid or alkali and after outer again arrange, supplies
Consume many, production cost height；Part wolfram element, molybdenum element are inevitably taken out of in waste water, and the wolfram element response rate is low；Wolframic acid
Substantial amounts of high bisulfate waste liquor is produced in sodium solution transformation process, and evaporative crystallization mother solution produces ammonia nitrogen waste water；Equipment investment is big, technique stream
Journey is long, and productivity ratio is relatively low, it is more difficult to realize continuous production.
Due to existing environmental protection standard more and more higher, the present invention proceeds from the reality, existing APT production line is carried out environmental protection with
The upgrading of production capacity, it is established that the high APT production line of a wastewater zero discharge and water circulation use profit, in energy-saving and emission-reduction and money
The aspects such as the efficient utilization in source all increase significantly.
Content of the invention
For the above-mentioned technical problem in correlation technique, the present invention proposes a kind of APT and produces wastewater recycling method, energy
A wastewater zero discharge and water circulation use rate high APT production line is enough set up.
For above-mentioned technical purpose is realized, the technical scheme is that and be achieved in that：
A kind of APT produces wastewater recycling method, the raffinate that the method is produced during preparing APT for extraction
Cycling utilization of wastewater is carried out, the method includes：
Step S1 causticization：The raffinate being stored in raffinate circulatory pool is delivered to causticization pulping tank, and to raffinate
Middle addition metering Calx carries out causticization, controls PH=10～14 in the causticization pulping tank；After reacted causticization serosity standing
Filter pressing is carried out, obtains liquid after causticization；
The slurrying of step S2：Liquid after the causticization that the Tungstic anhydride. of tungstenic more than 80% is obtained with step S1, by liquid：Gu=
4：1 carries out slurrying, and wherein Tungstic anhydride. granularity adds the silicon inhibitor of Tungstic anhydride. amount 1/15～1/20 in 180～200 mesh,
Stirring makes its equal homogenization, obtains pulp liquid；
Step S3 alkali soaks：The pulp liquid that step S2 is obtained is put in alkali leaching kettle carries out alkali leaching, the alkali leaching kettle steaming
Steam pressure control obtains reacted feed liquid in 0.1～0.4Mpa；
Further, the step S3 alkali leaching also includes：The liquid for completing after alkali leaching in alkali leaching kettle is heated up, when which
When 90 DEG C are warming up to, after insulation half an hour, by gas-liquid separation device, liquid are entered in underflow groove, and compressed air is pressed into
In underflow groove, underflow is lowered the temperature.
Further, the step S3 alkali leaching also includes：Filter pressing is carried out when underflow temperature drop is to 70 DEG C, after filter pressing is complete
With liquid or raffinate after the causticization, Tungstic anhydride. concentration and pH value in the filtrate after filter pressing is adjusted so as to be maintained at 110-
120g/L, PH=10～14.
Further, the step S3 alkali leaching also includes：Secondary filter is carried out to the filtrate after filter pressing, the fine straining after filtration
Liquid is entered in step S4 and carries out extractive reaction.
Step S4 is extracted：The feed liquid that step S3 is obtained is input into extraction tank, adds extractant to be extracted, adds during extraction
After the causticization for obtaining in S1, liquid adjusts pH value, makes raffinate PH be adjusted to 10～14, and the raffinate of generation enters raffinate circulation
Chi Zhong；Wherein feed liquid：Extractant=(1～2)：(2～3)；Raffinate after PH is adjusted is stored in raffinate circulatory pool, and circulates
Enter in step S1.
The back extraction of step S5：The reacted extractant of extraction tank is entered and is clarified in defecator in step s 4, after clarification
Liquid enter in back extraction groove and add back washing agent to carry out back extraction, to obtain strip liquor, wherein, feed liquid in step S4 and S5：Extraction
Take agent：Back washing agent=(1～2)：(2～3)：(0.1～1), the Tungstic anhydride. concentration in the strip liquor reaches 180～200g/
L；Extractant after back extraction is recycled in the extraction tank of step S4；
Step S6 is deoiled sulfuration：The strip liquor that step S5 is obtained is deoiled through carbon column, the liquid after deoiling
Body enters the ammonium sulfide for adding strip liquor volume 1/30 in vulcanization plant, stands after stirring, and obtains sulfuration strip liquor；
Further, also include molybdenum removal process in step S6：Sulfuration strip liquor after standing is added and is filled except molybdenum
Putting is carried out except molybdenum, described include accurate filter except molybdenum device, under the discharging opening of the accurate filter and packed moving bed
Portion's inlet connection, the sulfuration strip liquor is with 1～2m3The flow of/h is with the Special Resin in uplink mode end count reality moving bed
Except liquid after molybdenum must be removed after molybdenum, flow out through packed moving bed top liquid outlet.
Further, the top of the packed moving bed is provided with top and is provided with resin inlet, and bottom is provided with resin
Outlet, the resin outlet is connected with resin transfer device and exports negative molybdenum resin, and the negative molybdenum resin is obtained containing molybdenum after desorbing
Peak liquid, is then delivered to sink in molybdenum reactor, adjusts its PH=1～3 with concentrated sulphuric acid in heavy molybdenum reactor, precipitates molybdenum,
After filter pressing, molybdenum is entered in residue and carries out molybdenum recovery, obtains seasoning liquid.
Further, also include tungsten removal process in step S6：The seasoning liquid after secondary filter, through activity
After carbon post oil removing, then tungsten recovery is carried out through ion exchange column, in tungstenic peak liquid and step S3 that then desorbing is obtained
Feed liquid carry out mix homogeneously.
Step S7 is crystallized：The liquid that step S6 is obtained is added in crystallization kettle and carries out crystallization reaction, reacted crystalline solid
Solution is carried out liquid and is separated with crystal, and wherein, during crystallization, Steam pressure control is crystallized terminal point control and exists in 0～0.4Mpa
1.03～1.01；
Further, also include ammonia recovering process in step S7：Discharged during evaporative crystallization in the crystallization kettle
Ammonia, vapor recovered after, make ammonia and be used for preparing back washing agent, entering in step S5 carries out back extraction.
Further, tail washings of the negative molybdenum resin through producing in the tail washings produced by desorbing and tungsten removal process enters useless
In pond, it is evaporated by triple effect evaporator；During evaporation, steam pressure control is in 0.1～0.2Mpa, vacuum degree control-
0.03～-0.08Mpa.
Beneficial effects of the present invention：
The useful metal such as tungsten the 1st, in tail washings and molybdenum is recovered, and has both been avoided that the loss of tungsten, can increase its additional output value again,
So as to reach the purpose of lifting economic benefit；
2nd, the tail washings part that is discharged is recovered Posterior circle and is evaporated consumption using slurrying, another part is come, and steam is cold
It is used for after solidifying Water Sproading preparing back washing agent, so as to reach the purpose of wastewater zero discharge；
3rd, according to former technique, 80 DEG C or so need to be heated to steam during causticization, and the heating-up time needs 6-8 hour, existing
Stood by storage tank, good effect can be also reached, the utilization rate of Calx can reach 80%, so as to save steam；
4th, the APT for being produced can reach national 0 grade of standard.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to institute in embodiment
The accompanying drawing for using is needed to be briefly described, it should be apparent that, drawings in the following description are only some enforcements of the present invention
Example, for those of ordinary skill in the art, on the premise of not paying creative work, can also obtain according to these accompanying drawings
Obtain other accompanying drawings.
Fig. 1 is the flow chart of APT production wastewater recycling method described according to embodiments of the present invention.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, the every other embodiment obtained by those of ordinary skill in the art, belong to present invention protection
Scope.
Extraction is mainly used in wolframite, scheelite, tungsta ore deposit and tungsten waste material production APT.By black and white tungsten ore, tungsten
After miscellaneous ore deposit and the roasting of tungsten waste material elder generation, caustic digestion generates sodium tungstate solution again；Again through removal of impurities is filtered；The good sodium tungstate solution of remove impurity
Ammonium tungstate solution is obtained after extraction and back extraction；Ammonium tungstate solution obtains ammonium paratungstate product through evaporative crystallization again.
A kind of APT produces wastewater recycling method, using the high APT life of a wastewater zero discharge and water circulation use rate
Producing line, with the Tungstic anhydride. of tungstenic more than 80% as raw material by including at least pulping device, alkali bath unit, filter-pressing device, essence
Close defecator, extraction back extraction system, sulfuration degreaser, 0 grade of APT is produced except the apparatus such as molybdenum device, crystallization apparatus.
In addition, its auxiliary device includes：Causticization system, molybdenum retracting device, tungsten retracting device, ammonia recovery unit and triple effect evaporator
Deng the valuable materials such as the tungsten in ending liquid back and forth, molybdenum, ammonia and recycling and the evaporation process of tail washings, to reach wastewater zero discharge
Purpose with lifting economic benefit.
The basic conception being related in the method：
Solvent extraction：Metal ion or its compound is made to be proceeded in the liquid organic phase immiscible with water by aqueous solution, then
Metal is made to proceed to water phase by organic faciess using back washing agent.
Phase：Uniform parts in system with same physical properties and chemical composition.
Extractant：Can be with the organic solvent for being generated extracted species by extraction thing effect.
Extracted species：The compound for generating is reacted by extraction thing and extractant.
Raffinate：The water phase of remaining after extraction.
Back washing agent：Extracted species can be destroyed and make to be extracted thing and generate the reagent of material of being soluble in the aqueous phase.
Strip liquor：Water phase after back extraction.
The flow chart of the method as shown in figure 1, specific process step is as follows,：
1st, slurrying：Pulping device at least includes pulping tank, matching pump and connecting pipe, is wherein furnished with row above pulping tank
Hang, its own is connected with pump with liquid import and frame type stirring device after charging aperture, causticization, discharging opening, and matching pump is using compression
Air drives.
Concrete operations are：Liquid after the Tungstic anhydride. of tungstenic more than 80% and causticization is pressed liquid：Gu=4：1 puts into pulping tank
In, Tungstic anhydride. granularity adds the silicon inhibitor of Tungstic anhydride. amount 1/15～1/20 in 180～200 mesh, stirs 30 minutes, makes
Its equal homogenization, is then pumped in alkali leaching kettle.
2nd, alkali leaching：Alkali bath unit at least includes alkali leaching kettle, matching pump, underflow groove, gas-liquid separation device and connecting pipe, its
Carry on middle alkali leaching kettle into/discharge gate, exhaust-valve, compressed air piping, thermometer, pressure gauge, its discharging opening and gas-liquid separation
Device connects, and gas-liquid separation device is connected with underflow groove.
Concrete operations are：Alkali leaching carried out to the serosity for pumping into alkali leaching kettle, alkali leaching kettle Steam pressure control 0.1～
0.4Mpa；The liquid for completing after alkali leaching in alkali leaching kettle is heated up, when which is warming up to 90 DEG C, after insulation half an hour, is passed through
Gas-liquid separation device enters liquid in underflow groove, and in compressed air press-in underflow groove, underflow will be lowered the temperature.
3rd, filter pressing：Filter-pressing device at least includes filter press, matching pump, filtrate tank and connecting pipe, wherein sheet frame
Have liquid dish below filter press filter board, below liquid dish, unload cinder notch, liquid dish can flexibly push-and-pull from below filter press,
There is liquid outlet to be connected with filtrate tank on liquid dish, above filtrate tank, also carry tungstenic peak liquid feed pipe.
Concrete operations are：In the underflow groove slurry temperature drop to 70 DEG C with when carry out filter pressing, with after causticization after filter pressing is complete
Liquid or raffinate adjust Tungstic anhydride. concentration and pH value in filtrate (filtrate is sodium tungstate solution) so as to be maintained at 110-
120g/L, PH=10～14, filtrate is entered in filtrate tank.
4th, secondary filter：Precise filtering device at least includes accurate filter, smart filtrate tank and connecting pipe, accurate mistake
Filter charging aperture is connected with filtrate tank bottom discharge mouth in 3 pressure-filtering process.
Concrete operations are：Secondary filter is carried out to the filtrate after filter pressing, is then pumped in smart filtrate tank.
5th, extraction, back extraction：Extraction, back extraction system at least include extraction tank, defecator, back extraction groove, matching pump, head tank,
Lower tank and connecting pipe, wherein extraction tank are respectively provided with extractant import, fine straining liquid charging aperture, extractant outlet, raffinate
Outlet, fine straining liquid charging aperture is connected with smart filtrate tank in step 4 secondary filter, and raffinate outlet is connected with extract circulation
Pond.
Defecator import with extractant outlet be connected, defecator extractant export be connected with back extraction groove extractant import,
Back extraction groove is also with back washing agent import and back washing agent outlet, strip liquor outlet.Wherein, extraction tank, back extraction groove carry teeter chamber, instead
Extraction groove carries return duct, also adds liquid caustic soda (liquid after causticization) inlet pipe in the raffinate outlet level of extraction tank, convenient for adjusting
Raffinate pH value.
Concrete operations are：The fine straining liquid for filtering through essence is extracted in extraction tank, reacted raffinate is entered
In raffinate circulatory pool, and after adding causticization, liquid adjusts pH value；The clarified process of reacted extracted species feed liquid enters back extraction
Groove carries out back extraction.Back washing agent after stripping process is entered in back extraction groove by return duct through back washing agent outlet again and circulates profit again
With, and obtain strip liquor (ammonium tungstate solution).
The effect of this device is the transition for removing impurity and tungstates including at least including P, Si, As etc., i.e., by sodium salt
(sodium tungstate) is converted to ammonium salt (ammonium tungstate), wherein feed liquid：Extractant：Back washing agent=(1～2)：(2～3)：(0～1), passes through
Extraction back extraction device, the Tungstic anhydride. concentration in solution (strip liquor) can reach 180～200g/L, raffinate PH be adjusted to 10～
14.
6th, deoil sulfuration：Sulfuration degreaser at least includes carbon column, sulfur tank, matching pump and connecting pipe, wherein
Carbon column includes upper feed inlet, top emptying, bottom discharge mouth.
Concrete operations are：Strip liquor is entered through carbon column charging aperture, is flowed into transfer tank from bottom discharge mouth, then through pump
Pump in sulfur tank and vulcanized, the ammonium sulfide of about strip liquor volume 1/30 is added, after stirring, time of repose is no less than 24
Hour.
7th, molybdenum is removed：Except molybdenum device at least includes accurate filter, packed moving bed, vulcanization bed, resin transfer device and supporting
Pump and connecting pipe, wherein described 6 vulcanize the charging aperture of the sulfur tank bottom discharge mouth connection accurate filter in deoiling, accurate
The bottom charging aperture of the discharging opening connection packed moving bed of filter, the top of packed moving bed is provided with resin inlet, bottom
It is additionally provided with resin outlet and connects the resin inlet of resin carrier.Inlet, liquid outlet is provided with resin transfer device, its
Middle inlet is connected by threeway with accurate filter, its liquid outlet connection vulcanization bed upper resin import, and vulcanization bed is joined
There is compressed air.
Concrete operations are：Ammonium tungstate solution is with 1～2m3The flow of/h is with the extraordinary tree in uplink mode end count reality moving bed
Fat except after molybdenum high-purity ammonium tungstate solution (except liquid after molybdenum), through packed moving bed top liquid outlet from flowing into except liquid storage tank after molybdenum
In.
8th, crystallize：Crystallization apparatus at least include crystallization kettle, sucking filtration disk, mortejus, eluting column, wherein air exhauster, crystallization kettle
With charging aperture, observation port, bottom discharge mouth, steam vent, crystallize liquid solution and discharge from bottom discharge mouth, flow in sucking filtration disk,
The mortejus of sucking filtration disk connect band evacuation, draws liquid in mortejus, and crystal stays in the aerofluxuss in sucking filtration disk, on crystallization kettle
Mouth is connected with eluting column, and eluting column is connected with air exhauster, and during crystallization, the part ammonia in kettle, vapor are extracted out by air exhauster, warp
Eluting column absorbs.
Concrete operations are：Will except after molybdenum except after molybdenum liquid add in crystallization kettle and carry out crystallization reaction, reacted crystalline solid is molten
Liquid is carried out liquid and is separated with crystal, during crystallization Steam pressure control in 0～0.4Mpa, crystallize terminal point control 1.03～
1.01, primary crystallization mother solution is taken out to be pressed onto in secondary crystallization kettle by mortejus carries out recrystallization, and secondary crystallization mother solution is returned by tungsten
Receiving apparatus are processed further, and the APT that primary crystallization goes out is up to 0 grade of standard.Wherein, crystallization terminal refers to determine crystallization with densimeter
The density of the ammonium tungstate solution in kettle, when solution density reaches 1.03-1.01, it is possible to blowing.Its this density be by height
To low, the evaporative crystallization time is more long, and its density is lower, and the APT for crystallizing out is more.
9th, causticization：Causticization device at least includes raffinate circulatory pool, causticization slurrying pond, causticization serosity storage tank, pressure filter, joins
Set pump and connecting pipe, wherein causticization slurrying pond band frame type stirring, raffinate of the raffinate through extraction tank in 5 extractive reaction
Outlet is flowed in raffinate circulatory pool, and being pumped into pump carries out causticization in causticization slurrying pond, in causticization serosity pump causticization serosity storage tank
Standing.
Concrete operations are：Metering Calx being added in raffinate during causticization, control PH=10～14, pumps into the storage of causticization serosity
Filter pressing after 1～2 day being stood in groove, filtrate (liquid after causticization) is flowed into through liquid dish after causticization in liquid pool, and after causticization, liquid returns described 1
Slurrying in pulping device.
10th, molybdenum is reclaimed：Molybdenum retracting device includes heavy molybdenum reactor, chamber filter press, acid adjustment liquid storage tank, matching pump and connection
Pipeline, the molybdenum reactor bottom discharge gate that wherein sinks is connected by pump with the charging aperture of chamber filter press, is had below chamber filter press
Unload cinder notch.
Concrete operations are：Described 6 vulcanize negative molybdenum resin in operation of deoiling obtains the liquid of peak containing molybdenum after desorbing, uses concentrated sulphuric acid
Its PH=1～3 is adjusted in heavy molybdenum reactor, precipitate molybdenum, after chamber filter press filter pressing, molybdenum is entered in slag, and tungsten enters molten
In liquid and flow in acid adjustment liquid storage tank, seasoning liquid is obtained, is reclaimed through tungsten retracting device further.
11st, tungsten is reclaimed：Tungsten retracting device at least includes carbon column, accurate filter, ion exchange column, matching pump and pipe
In road, the wherein 10 molybdenum removal process, seasoning liquid storage tank is connected with accurate filter charging aperture, its discharging opening and carbon column
Its top feed mouth connects, and carbon column bottom discharge mouth is connected with ion exchange column its top feed mouth.
Concrete operations are：The seasoning liquid after secondary filter, after carbon column oil removing, then through ion exchange column
Tungsten recovery is carried out, the liquid of acquisition is added in the step 8 and carries out crystallization reaction.Secondary crystallization mother solution in the step 8 leads to
Cross after acid adjustment filter through accurate filter together with the tungstenic liquid in step 9 causticization, after carbon column oil removing, institute's tungstenic
It is ion exchanged post to be absorbed, the tungsten after absorption enters secondary filter in the step 4 after desorbing.
12nd, recovery ammonia：Ammonia recovery unit at least includes hydraulic jet pump and pipeline, step 8 wherein described in hydraulic jet pump
Middle crystallization kettle air vent connection, the most ammonias for being discharged during evaporative crystallization in step 8 crystallization, vapor are through water
Power ejector pump is entered in ammonia accumulator tank after absorbing, and carries out back extraction for preparing in the back washing agent entrance step 5.
Concrete operations are：After the ammonia that discharged during evaporative crystallization in the crystallization kettle, vapor are recovered, ammonia is made
Water is used for preparing back washing agent, and entering in the step 5 extraction back extraction device carries out back extraction.
13rd, triple effect evaporation：Step 7, the tail washings in 11 produced by desorbing, regenerating resin are entered in wastewater disposal basin, by triple effect
Vaporizer is evaporated.During evaporation, steam pressure controls in 0.1～0.2Mpa, and vacuum degree control is in -0.03～-0.08Mpa.
By the APT production method of the present invention, it is possible to achieve：
The useful metal such as tungsten the 1st, in tail washings and molybdenum is recovered, and has both been avoided that the loss of tungsten, can increase its additional output value again,
So as to reach the purpose of lifting economic benefit；
2nd, the tail washings part that is discharged is recovered Posterior circle and is evaporated consumption using slurrying, another part is come, and steam is cold
It is used for after solidifying Water Sproading preparing back washing agent, so as to reach the purpose of wastewater zero discharge；
3rd, according to former technique, 80 DEG C or so need to be heated to steam during causticization, and the heating-up time needs 6-8 hour, existing
Stood by storage tank, good effect can be also reached, the utilization rate of Calx can reach 80%, so as to save steam；
4th, the APT for being produced can reach national 0 grade of standard.
Presently preferred embodiments of the present invention is the foregoing is only, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement that is made etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of APT produces wastewater recycling method, it is characterised in that the method is produced during preparing APT for extraction
Raw raffinate carries out cycling utilization of wastewater, and the method includes：
Step S1 causticization：The raffinate being stored in raffinate circulatory pool is delivered to causticization pulping tank, and is added in raffinate
Entering to measure Calx carries out causticization, controls PH=10～14 in the causticization pulping tank；Carry out after reacted causticization serosity standing
Filter pressing, obtains liquid after causticization；
The slurrying of step S2：Liquid after the causticization that the Tungstic anhydride. of tungstenic more than 80% is obtained with step S1, by liquid：Gu=4：1
Slurrying is carried out, wherein Tungstic anhydride. granularity adds the silicon inhibitor of Tungstic anhydride. amount 1/15～1/20, stirring in 180～200 mesh
Its equal homogenization is made, obtains pulp liquid；
Step S3 alkali soaks：The pulp liquid that step S2 is obtained puts in alkali leaching kettle and carries out alkali leaching, and the alkali soaks kettle vapour pressure
Power control obtains reacted feed liquid in 0.1～0.4Mpa；
Step S4 is extracted：The feed liquid that step S3 is obtained is input into extraction tank, adds extractant to be extracted, adds in S1 during extraction
After the causticization of acquisition, liquid adjusts pH value, makes raffinate PH be adjusted to 10～14, and the raffinate of generation is entered in raffinate circulatory pool；
Wherein feed liquid：Extractant=(1～2)：(2～3)；Raffinate after PH is adjusted is stored in raffinate circulatory pool, and is recycled into
In step S1.
2. APT according to claim 1 produces wastewater recycling method, it is characterised in that the step S3 alkali leaching is also
Including：The liquid for completing after alkali leaching in alkali leaching kettle is heated up, when which is warming up to 90 DEG C, after insulation half an hour, by gas
Liquid separating apparatus enter liquid in underflow groove, and in compressed air press-in underflow groove, underflow will be lowered the temperature.
3. APT according to claim 2 produces wastewater recycling method, it is characterised in that the step S3 alkali leaching is also
Including：Filter pressing is carried out when underflow temperature drop is to 70 DEG C, with liquid or raffinate after the causticization after filter pressing is complete, after adjusting filter pressing
Filtrate in Tungstic anhydride. concentration and pH value so as to be maintained at 110-120g/L, PH=10～14.
4. APT according to claim 3 produces wastewater recycling method, it is characterised in that the step S3 alkali leaching is also
Including：Secondary filter is carried out to the filtrate after filter pressing, the fine straining liquid after filtration is entered in step S4 and carries out extractive reaction.
5. APT according to claim 1 produces wastewater recycling method, it is characterised in that the method also includes：
The back extraction of step S5：The reacted extractant of extraction tank is entered and is clarified in defecator in step s 4, the liquid after clarification
Body is entered in back extraction groove and adds back washing agent to carry out back extraction, to obtain strip liquor, wherein, feed liquid in step S4 and S5：Extractant：
Back washing agent=(1～2)：(2～3)：(0.1～1), the Tungstic anhydride. concentration in the strip liquor reaches 180～200g/L；Back extraction
Extractant afterwards is recycled in the extraction tank of step S4；
Step S6 is deoiled sulfuration：The strip liquor that step S5 is obtained is deoiled through carbon column, and the liquid after deoiling enters
Enter in vulcanization plant, the ammonium sulfide of strip liquor volume 1/30 is added, stand after stirring, obtain sulfuration strip liquor；
Step S7 is crystallized：The liquid that step S6 is obtained is added in crystallization kettle and carries out crystallization reaction, reacted crystallization liquid solution
Carry out liquid to separate with crystal, wherein, during crystallization Steam pressure control in 0～0.4Mpa, crystallize terminal point control 1.03～
1.01.
6. APT according to claim 5 produces wastewater recycling method, it is characterised in that also wrap in step S6
Include molybdenum removal process：Sulfuration strip liquor after standing is added to be carried out except molybdenum except molybdenum device, described includes accurate mistake except molybdenum device
Filter, the discharging opening of the accurate filter is connected with the bottom inlet of packed moving bed, the sulfuration strip liquor with 1～
2m3The flow of/h is removed after molybdenum with the Special Resin in uplink mode end count reality moving bed and must remove liquid after molybdenum, through on packed moving bed
Portion's liquid outlet flows out.
7. APT according to claim 6 produces wastewater recycling method, it is characterised in that the packed moving bed
Top is provided with top and is provided with resin inlet, and bottom is provided with resin outlet, and the resin outlet is connected with resin transfer device
And negative molybdenum resin is exported, the negative molybdenum resin obtains the liquid of peak containing molybdenum after desorbing, is then delivered to sink in molybdenum reactor, with dense
Sulphuric acid adjusts its PH=1～3 in heavy molybdenum reactor, precipitates molybdenum, and after filter pressing, molybdenum is entered in residue and carries out molybdenum recovery, is obtained
To seasoning liquid.
8. APT according to claim 7 produces wastewater recycling method, it is characterised in that also wrap in step S6
Include tungsten removal process：The seasoning liquid after carbon column oil removing, then carries out tungsten through ion exchange column after secondary filter
Reclaim, the tungstenic peak liquid that then desorbing is obtained is mixed homogeneously with the feed liquid in step S3.
9. APT according to claim 8 produces wastewater recycling method, it is characterised in that also wrap in step S7
Include ammonia recovering process：After the ammonia that discharged during evaporative crystallization in the crystallization kettle, vapor are recovered, make ammonia and be used for
Back washing agent is prepared, entering in step S5 carries out back extraction.
10. APT according to claim 9 produces wastewater recycling method, it is characterised in that the negative molybdenum resin is through solution
The tail washings for producing in tail washings and tungsten removal process produced by inhaling is entered in wastewater disposal basin, is evaporated by triple effect evaporator；Steam
When sending out, steam pressure controls in 0.1～0.2Mpa, and vacuum degree control is in -0.03～-0.08Mpa.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107641724A (en) * | 2017-08-25 | 2018-01-30 | 洛阳栾川钼业集团股份有限公司 | One kind improves WO in scheelite3The method of leaching rate |
| CN108179270A (en) * | 2017-12-18 | 2018-06-19 | 洛阳栾川钼业集团股份有限公司 | A kind of method of silicone content in reduction sodium tungstate solution |
| CN108706634A (en) * | 2018-06-12 | 2018-10-26 | 崇义章源钨业股份有限公司 | Purify the device and method of ammonium tungstate solution |
| CN109825725A (en) * | 2019-03-25 | 2019-05-31 | 湖南懋天世纪新材料有限公司 | A kind of method of comprehensive utilization of tungstenic causticization slag |
| CN111455172A (en) * | 2020-04-15 | 2020-07-28 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
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| GUIQING ZHANG,ETC: "a novel process for tungsten hydrometallurgybased on direct solvent extraction in alkaline medium", 《HYDROMETALLURGY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641724A (en) * | 2017-08-25 | 2018-01-30 | 洛阳栾川钼业集团股份有限公司 | One kind improves WO in scheelite3The method of leaching rate |
| CN108179270A (en) * | 2017-12-18 | 2018-06-19 | 洛阳栾川钼业集团股份有限公司 | A kind of method of silicone content in reduction sodium tungstate solution |
| CN108706634A (en) * | 2018-06-12 | 2018-10-26 | 崇义章源钨业股份有限公司 | Purify the device and method of ammonium tungstate solution |
| CN108706634B (en) * | 2018-06-12 | 2021-07-16 | 崇义章源钨业股份有限公司 | Apparatus and method for purifying ammonium tungstate solution |
| CN109825725A (en) * | 2019-03-25 | 2019-05-31 | 湖南懋天世纪新材料有限公司 | A kind of method of comprehensive utilization of tungstenic causticization slag |
| CN111455172A (en) * | 2020-04-15 | 2020-07-28 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
| CN111455172B (en) * | 2020-04-15 | 2022-05-06 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
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Denomination of invention: APT (ammonium paratungstate) production wastewater recycling method Effective date of registration: 20200616 Granted publication date: 20190906 Pledgee: Huarong Bank of Xiangjiang Limited by Share Ltd. Yiyang branch Pledgor: HUNAN MAOTIAN SHIJIE NEW MATERIALS Co.,Ltd. Registration number: Y2020980003142 |
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