CN106430787B - A kind of APT production wastewater recycling method - Google Patents

A kind of APT production wastewater recycling method Download PDF

Info

Publication number
CN106430787B
CN106430787B CN201610985109.4A CN201610985109A CN106430787B CN 106430787 B CN106430787 B CN 106430787B CN 201610985109 A CN201610985109 A CN 201610985109A CN 106430787 B CN106430787 B CN 106430787B
Authority
CN
China
Prior art keywords
liquid
molybdenum
causticization
apt
raffinate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610985109.4A
Other languages
Chinese (zh)
Other versions
CN106430787A (en
Inventor
李湘军
田吉英
蒋纯
曹育龙
曹成
蒋明
王琪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Maotian Shijie New Materials Co Ltd
Original Assignee
Hunan Maotian Shijie New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Maotian Shijie New Materials Co Ltd filed Critical Hunan Maotian Shijie New Materials Co Ltd
Priority to CN201610985109.4A priority Critical patent/CN106430787B/en
Publication of CN106430787A publication Critical patent/CN106430787A/en
Application granted granted Critical
Publication of CN106430787B publication Critical patent/CN106430787B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/03—Pressure
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Physical Water Treatments (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

The invention discloses a kind of APT to produce wastewater recycling method, a wastewater zero discharge and the high APT production line of water circulation use rate can be established, the tungsten that may be implemented in tail washings is recovered with useful metals such as molybdenums, both it had been avoided that the loss of tungsten, it can increase its additional output value again, to achieve the purpose that promote economic benefit；The tail washings a part being discharged recycles after being recovered carrys out slurrying, and another part is evaporated consumption, is used to prepare stripping agent after reclamation of condensate water, to achieve the purpose that wastewater zero discharge；Causticization process changes previous steam-heated mode and by storage tank stewing process, can also reach good effect, the utilization rate of lime can reach 80%, to save steam；APT produced can reach national 0 grade standard.

Description

A kind of APT production wastewater recycling method
Technical field
The present invention relates to resource reclaims to recycle field, it particularly relates to which a kind of APT produces cycling utilization of wastewater side Method.
Background technique
In the prior art, purification and impurity removal produces ammonium paratungstate APT (Ammonium from sodium tungstate solution Paratungstate) there are three types of the commercial runs of solution, i.e., classical chemical method, ion-exchange and solvent extraction, wherein Classical chemical method is due to consuming big, the low less use at present of yield.Ion-exchange and solvent extraction respectively have its advantage And deficiency, each producer's view concrete condition selection.
Ion-exchange, can be while transition except the anionic impurities such as dephosphorization, arsenic, silicon, work compared with solvent extraction Skill process is short, and operation is simpler, but haves the shortcomings that water consumption is big and wastewater discharge is big, in addition, the crystallization of ion-exchange Mother liquor directly can not return to main flow and need to set auxiliary process recycling.The advantages of solvent extraction under acid condition, is process Water consumption and wastewater discharge are small, for advantageous with the area that water is limited and draining is difficult.But it is molten under existing acid condition There is also deficiencies, i.e. extraction process only to play transition without impurity removal function for agent extraction, and removal of impurities still uses chemical precipitation method, because This process is longer, and has waste residue generation, 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 the main of APT and includes the following steps: to obtain by caustic soda or soda leaching tungsten mineral material Obtain coarse sodium tungstate；It is cleaned and is made the transition by solvent extraction, obtain pure tungsten acid ammonium solution；Again by evaporative crystallization, APT is obtained Product.
Environmentally friendly zero-emission and water circulation use rate are extremely difficult to by the purifying and impurity-removing method that solvent extraction prepares APT Standard.At least there is following technical problem in the prior art: waste water discharge opening must be arranged, waste water pollution problem can not thorough root It removes；Supplies are mostly expendable consumed product, and the leaching agent of leaching process is excessively used, these supplies are in corresponding work It either directly outlet or is needed using outlet again, supplies after corresponding acid or alkali neutralization after skill step reaction Consume more, high production cost；Inevitably take part wolfram element, molybdenum element out of in waste water, the wolfram element rate of recovery is low；Wolframic acid A large amount of high bisulfate waste liquor is generated in sodium solution transformation process, evaporative crystallization mother liquor generates ammonia nitrogen waste water；Equipment investment is big, technique stream Journey is long, and productivity is lower, it is more difficult to realize continuous production.
Since existing environmental protection standard is higher and higher, the present invention proceeds from the reality, to existing APT production line carry out environmental protection with The upgrading of production capacity, it is established that a wastewater zero discharge and the sharp high APT production line of water circulation use, in energy-saving and emission-reduction and money Efficiently utilizing etc. for source all increases significantly.
Summary of the invention
For above-mentioned technical problem in the related technology, the present invention proposes a kind of APT production wastewater recycling method, energy Enough establish a wastewater zero discharge and the high APT production line of water circulation use rate.
To realize the above-mentioned technical purpose, the technical scheme of the present invention is realized as follows:
A kind of APT production wastewater recycling method, this method prepare the raffinate generated during APT for extraction Cycling utilization of wastewater is carried out, this method comprises:
Step S1 causticization: being delivered to causticization pulping tank for the raffinate being stored in raffinate circulatory pool, and to raffinate Middle addition metering lime carries out causticization, controls PH=10~14 in the causticization pulping tank；After causticization slurries after reaction are stood Filters pressing is carried out, liquid after causticization is obtained；
Step S2 slurrying: liquid after the causticization that the tungstic acid and step S1 of 80% or more tungstenic obtain, by liquid: Gu= 4:1 carries out slurrying, and wherein the silicon inhibitor of tungstic acid amount 1/15~1/20 is added in 180~200 mesh in tungstic acid granularity, Stirring makes its equal homogenization, obtains pulp liquid；
The leaching of step S3 alkali: alkali leaching is carried out in the pulp liquid investment alkali leaching kettle that step S2 is obtained, the alkali leaching kettle steams Steam pressure controls the feed liquid in 0.1~0.4Mpa, after being reacted；
Further, the step S3 alkali leaching further include: heat up to the liquid after alkali soaks is completed in alkali leaching kettle, when it When being warming up to 90 DEG C, after keeping the temperature half an hour, liquid is discharged into underflow slot by gas-liquid separation device, and compressed air is pressed into Cool down in underflow slot to underflow.
Further, the step S3 alkali leaching further include: filters pressing is carried out when underflow temperature drops to 70 DEG C, after filters pressing is complete With liquid or raffinate after the causticization, tungstic acid concentration and pH value in the filtrate after adjusting filters pressing keep it in 110- 120g/L, PH=10~14.
Further, the step S3 alkali leaching further include: secondary filter, filtered refined filtration are carried out to the filtrate after filters pressing Liquid, which enters in the step S4, carries out extraction reaction.
Step S4 extraction: the feed liquid that step S3 is obtained inputs extraction tank, and extractant is added and is extracted, and when extraction is added Liquid adjusts pH value after the causticization obtained in S1, so that raffinate PH is adjusted to 10~14, 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 recycles It enters step in S1.
Step S5 back extraction: the extractant after extraction tank reaction, which enters in defecator, in step s 4 is clarified, after clarification Liquid enter and stripping agent is added in back extraction slot is stripped, to obtain strip liquor, wherein the feed liquid in step S4 and S5: extraction Take agent: stripping agent=(1~2): (2~3): (0.1~1), the tungstic acid concentration in the strip liquor reach 180~200g/ L；Extractant after back extraction is recycled into the extraction tank of step S4；
Step S6 deoils vulcanization: the strip liquor that step S5 is obtained deoils through carbon column, the liquid after deoiling Body enters in vulcanization plant, and the ammonium sulfide of strip liquor volume 1/30 is added, stands after mixing evenly, obtains vulcanization strip liquor；
Further, further include molybdenum removal process in the step S6: the vulcanization strip liquor after standing is added except molybdenum fills It sets and carries out except molybdenum, the molybdenum device that removes includes accurate filter, under the discharge port and packed moving bed of the accurate filter The connection of portion's inlet, the vulcanization strip liquor is with 1~2m3The flow of/h is with uplink mode through the Special Resin in packed moving bed Except being obtained after molybdenum except liquid after molybdenum, flowed 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 lower part is provided with resin Outlet, the resin outlet are connected with resin transfer device and export negative molybdenum resin, and the negative molybdenum resin is obtained after desorbing containing molybdenum Peak liquid is then delivered in heavy molybdenum reaction kettle, is adjusted its PH=1~3 in heavy molybdenum reaction kettle with the concentrated sulfuric acid, is precipitated molybdenum, After filters pressing, molybdenum enters progress molybdenum recycling in residue, obtains seasoning liquid.
Further, further include tungsten removal process in the step S6: the seasoning liquid is after secondary filter, through activity After carbon column oil removing, tungsten recycling is carried out using ion exchange column, is then desorbed in the tungstenic peak liquid and the step S3 of acquisition Feed liquid carry out it is uniformly mixed.
Step S7 crystallization: the liquid that step S6 is obtained being added in crystallization kettle and carries out crystallization reaction, the crystalline solid after reaction The separation of solution progress liquid and crystal, wherein Steam pressure control crystallizes terminal point control and exist in 0~0.4Mpa when crystallization 1.03~1.01；
Further, further include ammonia recovering process in the step S7: being released when evaporative crystallization in the crystallization kettle Ammonia, vapor it is recovered after, production ammonium hydroxide is used to prepare stripping agent, into being stripped in the step S5.
Further, tail washings of the negative molybdenum resin through generating in tail washings caused by desorption and tungsten removal process is discharged into useless In pond, it is evaporated by triple effect evaporator；Steam pressure control is in 0.1~0.2Mpa when evaporation, vacuum degree control- 0.03~-0.08Mpa.
Beneficial effects of the present invention:
1, the useful metals such as the tungsten in tail washings and molybdenum are recovered, and have not only been avoided that the loss of tungsten, but also can increase its additional output value, To achieve the purpose that promote economic benefit；
2, the tail washings a part being discharged recycles after being recovered carrys out slurrying, and another part is evaporated consumption, and steam is cold It is used to prepare stripping agent after condensate recycling, to achieve the purpose that wastewater zero discharge；
3, according to pervious technique, when causticization, need to be heated to 80 DEG C or so with steam, and the heating-up time needs 6-8 hours, existing It is stood by storage tank, can also reach good effect, the utilization rate of lime can reach 80%, to save steam；
4, APT produced can reach national 0 grade standard.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings Obtain other attached drawings.
Fig. 1 is the flow chart of the APT production wastewater recycling method described according to embodiments of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art's every other embodiment obtained belong to what the present invention protected Range.
Extraction is mainly used in the miscellaneous mine of wolframite, scheelite, tungsten and tungsten waste material production APT.Pass through black and white tungsten ore, tungsten Miscellaneous mine and tungsten waste material first roast after again caustic digestion generate sodium tungstate solution；Using removal filtration；The sodium tungstate solution to have cleaned Ammonium tungstate solution is obtained after extraction and back extraction；Ammonium tungstate solution obtains ammonium paratungstate product using evaporative crystallization.
A kind of APT production wastewater recycling method, it is raw using the high APT of a wastewater zero discharge and water circulation use rate Producing line is raw material by including at least pulping device, alkali bath unit, filter-pressing device, essence using the tungstic acid of 80% or more tungstenic Close filter device, vulcanization degreaser, produces 0 grade of APT except apparatus such as molybdenum device, crystallization apparatus at extraction back extraction system. In addition to this, auxiliary device includes: causticization system, molybdenum recyclable device, tungsten recyclable device, ammonia recovery unit and triple effect evaporator Deng the recycling and evaporation process of the valuable materials such as tungsten, molybdenum, ammonia and tail washings in the liquid that back and forth finishes up, to reach wastewater zero discharge With the purpose for promoting economic benefit.
The basic conception being related in this method:
Solvent extraction: being transferred to metal ion or its compound by aqueous solution in the liquid organic phase immiscible with water, then Metal is set to be transferred to water phase by organic phase using stripping agent.
Phase: with the uniform parts of same physical properties and chemical component in system.
Extractant: can with by extraction object act on generate extracted species organic solvent.
Extracted species: the compound generated is reacted with extractant by extraction object.
Raffinate: remaining water phase after extraction.
Stripping agent: extracted species can be destroyed and make to be extracted object generating the reagent of substance of being soluble in the aqueous phase.
Strip liquor: the water phase after back extraction.
The flow chart of this method as shown in Figure 1, specific processing step is as follows:
1, slurrying: pulping device includes at least pulping tank, matching pump and connecting pipe, wherein equipped with row above pulping tank It hangs, its own is connected with liquid import and frame type stirring device after feed inlet, causticization, discharge port and pump, and matching pump is using compression Air driving.
Concrete operations are as follows: liquid after the tungstic acid of 80% or more tungstenic and causticization is pressed into liquid: Gu=4:1 puts into pulping tank In, the silicon inhibitor of tungstic acid amount 1/15~1/20 is added in 180~200 mesh in tungstic acid granularity, stirs 30 minutes, makes Its equal homogenization is then pumped into alkali leaching kettle.
2, alkali soaks: alkali bath unit includes at least alkali leaching kettle, matching pump, underflow slot, gas-liquid separation device and connecting pipe, It has on middle alkali leaching kettle into/discharge gate, exhaust-valve, compressed air pipe, thermometer, pressure gauge, discharge port and gas-liquid separation Device connection, gas-liquid separation device are connect with underflow slot.
Concrete operations are as follows: alkali leaching carried out to the slurries for being pumped into alkali leaching kettle, alkali soak kettle Steam pressure control 0.1~ 0.4Mpa；It heats up to the liquid after alkali soaks is completed in alkali leaching kettle, when it is warming up to 90 DEG C, after keeping the temperature half an hour, passes through Liquid is discharged into underflow slot by gas-liquid separation device, and compressed air is pressed into underflow slot and is cooled down to underflow.
3, filters pressing: filter-pressing device includes at least plate and frame filter press, matching pump, filtrate tank and connecting pipe, wherein sheet frame There is liquid dish below filter press filter board, cinder notch is unloaded below liquid dish, liquid dish can be pushed and pulled flexibly from below plate and frame filter press, There is liquid outlet to be connected with filtrate tank on liquid dish, tungstenic peak liquid feed pipe is also had above filtrate tank.
Concrete operations are as follows: when slurry temperature in underflow slot drop to 70 DEG C with when carry out filters pressing, with after causticization after filters pressing is complete Liquid or raffinate adjust tungstic acid concentration and pH value in filtrate (filtrate is sodium tungstate solution), keep it in 110- 120g/L, PH=10~14, filtrate enters in filtrate tank.
4, secondary filter: precise filtering device includes at least accurate filter, smart filtrate tank and connecting pipe, accurate mistake Filter feed inlet is connect with filtrate tank bottom discharge port in 3 pressure-filtering process.
Concrete operations are as follows: secondary filter is carried out to the filtrate after filters pressing, is then pumped into smart filtrate tank.
5, extract, be stripped: extraction, back extraction system include at least extraction tank, defecator, back extraction slot, matching pump, head tank, Lower tank and connecting pipe, wherein extraction tank is respectively provided with extractant import, refined filtration liquid feed inlet, extractant outlet, raffinate Outlet, refined filtration liquid feed inlet are connected with filtrate tank smart in step 4 secondary filter, and raffinate outlet is connected with extract liquor circulation Pond.
Defecator import and extractant export connect, defecator extractant outlet be stripped the import of slot extractant connect, Back extraction slot also has stripping agent import and stripping agent outlet, strip liquor outlet.Wherein, extraction tank, back extraction slot have teeter chamber, instead Extract slot and have return pipe, also adds liquid alkaline (liquid after causticization) inlet pipe in the raffinate outlet grade of extraction tank, it is convenient to be used to adjust Raffinate pH value.
Concrete operations are as follows: will be extracted in extraction tank by the refined filtration liquid of essence filtering, the raffinate after reaction enters In raffinate circulatory pool, and liquid adjusting pH value after causticization is added；The clarified process of extracted species feed liquid after reaction enters back extraction Slot is stripped.Stripping agent after stripping process exports to be entered in back extraction slot by return pipe again by stripping agent recycles benefit again With, and obtain strip liquor (ammonium tungstate solution).
The effect of this device is to remove the transition of impurity and tungstates including including at least P, Si, As etc., i.e., by sodium salt (sodium tungstate) is converted to ammonium salt (ammonium tungstate), wherein feed liquid: extractant: stripping agent=(1~2): (2~3): (0~1) is passed through Back extraction device is extracted, the tungstic acid concentration in solution (strip liquor) can reach 180~200g/L, and raffinate PH is adjusted to 10~ 14。
6, deoil vulcanization: vulcanization degreaser includes at least carbon column, sulfur tank, matching pump and connecting pipe, wherein Carbon column includes upper feed inlet, top emptying, bottom discharge port.
Concrete operations are as follows: strip liquor enters through carbon column feed inlet, flows into transfer tank from bottom discharge port, then through pumping It is pumped into sulfur tank and is vulcanized, the ammonium sulfide of about strip liquor volume 1/30 is added, time of repose is no less than 24 after mixing evenly Hour.
7, molybdenum is removed: except molybdenum device includes at least accurate filter, packed moving bed, vulcanization bed, resin transfer device and mating Pump and connecting pipe, wherein described 6 vulcanize the feed inlet of the connection accurate filter of the sulfur tank bottom discharge port in deoiling, it is accurate The discharge port of filter connects the lower part feed inlet of packed moving bed, is provided with resin inlet, bottom at the top of packed moving bed It is additionally provided with resin outlet and connects the resin inlet of resin conveyer.Inlet, liquid outlet are provided on resin transfer device, Middle inlet is connect with accurate filter by threeway, and liquid outlet connects the import of vulcanization bed upper resin, and vulcanization bed is matched There is compressed air.
Concrete operations are as follows: ammonium tungstate solution is with 1~2m3The flow of/h is set with uplink mode through the special type in packed moving bed Rouge obtains high-purity ammonium tungstate solution (except liquid after molybdenum), the liquid storage tank after packed moving bed top liquid outlet is flowed into except molybdenum certainly after removing molybdenum In.
8, crystallize: crystallization apparatus includes at least crystallization kettle, filters disk, mortejus, eluting column, exhaust fan, wherein crystallization kettle With feed inlet, peep hole, bottom discharge port, gas vent, crystallizes liquid solution and is discharged from bottom discharge port, flow into and filter in disk, The mortejus that disk connecting band vacuumizes is filtered, is drawn liquid into mortejus, crystal, which stays in, to be filtered in disk, the exhaust on crystallization kettle Mouthful connect with eluting column, eluting column is connect with exhaust fan, and exhaust fan passes through the part ammonia in kettle, vapor extraction when crystallization Eluting column absorbs.
Concrete operations are as follows: will be except, except crystallization reaction is carried out in liquid addition crystallization kettle after molybdenum, the crystalline solid after reaction is molten after molybdenum Liquid carries out the separation of liquid and crystal, when crystallization Steam pressure control in 0~0.4Mpa, crystallize terminal point control 1.03~ 1.01, primary crystallization mother liquor is pressed onto secondary crystallization kettle by mortejus pumping and is recrystallized, and secondary crystallization mother liquor is returned by tungsten Receiving apparatus is further processed, and the APT that primary crystallization goes out is up to 0 grade standard.Wherein, crystallization terminal refers to be measured with densitometer and crystallize The density of ammonium tungstate solution in kettle, when solution density reaches 1.03-1.01, so that it may blowing.Its this density is by height To low, the evaporative crystallization time is more long, and density is lower, and the APT crystallized out is more.
9, causticization: causticization device includes at least raffinate circulatory pool, causticization slurrying pond, causticization slurries storage tank, filter press, matches Set pump and connecting pipe, wherein causticization slurrying pond is with frame type stirring, raffinate of the raffinate through extraction tank in the 5 extraction reaction Outlet flows into raffinate circulatory pool, is pumped into causticization slurrying pond with pump and carries out causticization, and causticization slurries pump in causticization slurries storage tank It stands.
Concrete operations are as follows: metering lime is added when causticization into raffinate, controls PH=10~14, is pumped into the storage of causticization slurries Filters pressing after standing 1~2 day in slot, filtrate (liquid after causticization) is after liquid dish flows into causticization in liquid pool, and liquid returns to described 1 after causticization Slurrying in pulping device.
10, molybdenum recycles: molybdenum recyclable device includes heavy molybdenum reaction kettle, chamber filter press, adjusts acid solution storage tank, matching pump and connection Pipeline, wherein the feed inlet of heavy molybdenum reactor bottom discharge gate and chamber filter press, by pump connection, chamber filter press lower section has Unload cinder notch.
Concrete operations are as follows: described 6 vulcanize negative molybdenum resin in operation of deoiling obtains the liquid of peak containing molybdenum after desorbing, and uses the concentrated sulfuric acid Its PH=1~3 is adjusted in heavy molybdenum reaction kettle, precipitates molybdenum, after chamber filter press filters pressing, molybdenum enters in slag, and tungsten enters molten It in liquid and flows into tune acid solution storage tank, obtains seasoning liquid, further recycled through tungsten recyclable device.
11, tungsten recycles: tungsten recyclable device includes at least carbon column, accurate filter, ion exchange column, matching pump and pipe Road, wherein seasoning liquid storage tank is connect with accurate filter feed inlet in the 10 molybdenum removal process, discharge port and carbon column The connection of top feed mouth, carbon column bottom discharge port are connect with ion exchange column top feed mouth.
Concrete operations are as follows: the seasoning liquid is after secondary filter, after carbon column oil removing, using ion exchange column Tungsten recycling is carried out, the liquid of acquisition, which is added in the step 8, carries out crystallization reaction.Secondary crystallization mother liquor in the step 8 is logical Through accurate filter filtering, after carbon column oil removing together with the tungstenic liquid in step 9 causticization after toning acid, institute's tungstenic It is ion exchanged column to be absorbed, the tungsten after absorption enters secondary filter in the step 4 after desorbing.
12, recovery ammonia: ammonia recovery unit includes at least hydraulic jet pump and pipeline, wherein step 8 described in hydraulic jet pump The connection of middle crystallization kettle exhaust outlet, the most ammonias released in step 8 crystallization when evaporative crystallization, vapor are through water Power jet pump is discharged into ammonium hydroxide accumulator tank after absorbing, for preparing stripping agent into being stripped in the step 5.
Concrete operations are as follows: after ammonia, the vapor released when evaporative crystallization in the crystallization kettle is recovered, make ammonia Water is used to prepare stripping agent, extracts in back extraction device and is stripped into the step 5.
13, triple effect evaporation: step 7, desorption in 11, tail washings caused by regenerating resin are discharged into wastewater disposal basin, pass through triple effect Evaporator is evaporated.Steam pressure control is in 0.1~0.2Mpa when evaporation, and vacuum degree control is in -0.03~-0.08Mpa.
APT production method through the invention, may be implemented:
1, the useful metals such as the tungsten in tail washings and molybdenum are recovered, and have not only been avoided that the loss of tungsten, but also can increase its additional output value, To achieve the purpose that promote economic benefit；
2, the tail washings a part being discharged recycles after being recovered carrys out slurrying, and another part is evaporated consumption, and steam is cold It is used to prepare stripping agent after condensate recycling, to achieve the purpose that wastewater zero discharge；
3, according to pervious technique, when causticization, need to be heated to 80 DEG C or so with steam, and the heating-up time needs 6-8 hours, existing It is stood by storage tank, can also reach good effect, the utilization rate of lime can reach 80%, to save steam；
4, APT produced can reach national 0 grade standard.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of APT produces wastewater recycling method, which is characterized in that this method is for production during extraction preparation APT Raw raffinate carries out cycling utilization of wastewater, and this method comprises the steps of:
Step S1 causticization: being delivered to causticization pulping tank for the raffinate being stored in raffinate circulatory pool, and adds into raffinate Enter to measure lime and carry out causticization, controls PH=10~14 in the causticization pulping tank；Causticization slurries after reaction carry out after standing Filters pressing obtains liquid after causticization；
Step S2 slurrying: liquid after the causticization that the tungstic acid and step S1 of 80% or more tungstenic obtain, by liquid: Gu=4:1 Slurrying is carried out, wherein the silicon inhibitor of tungstic acid amount 1/15~1/20, stirring is added in 180~200 mesh in tungstic acid granularity Make its equal homogenization, obtains pulp liquid；
The leaching of step S3 alkali: alkali leaching is carried out in the pulp liquid investment alkali leaching kettle that step S2 is obtained, the alkali soaks kettle vapour pressure Power controls the feed liquid in 0.1~0.4Mpa, after being reacted；
Step S4 extraction: the feed liquid that step S3 is obtained inputs extraction tank, and extractant is added and is extracted, and when extraction is added in S1 Liquid adjusts pH value after the causticization of acquisition, so that raffinate PH is adjusted to 10~14, the raffinate of generation enters 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；
Step S5 back extraction: the extractant after extraction tank reaction, which enters in defecator, in step s 4 is clarified, the liquid after clarification Body enters addition stripping agent in back extraction slot and is stripped, to obtain strip liquor, wherein the feed liquid in step S4 and S5: extractant: Stripping agent=(1~2): (2~3): (0.1~1), the tungstic acid concentration in the strip liquor reach 180~200g/L；Back extraction Extractant afterwards is recycled into the extraction tank of step S4；
Step S6 deoils vulcanization: the strip liquor that step S5 is obtained deoils through carbon column, the liquid after deoiling into Enter in vulcanization plant, the ammonium sulfide of strip liquor volume 1/30 is added, stands after mixing evenly, obtains vulcanization strip liquor；
Step S7 crystallization: the liquid that step S6 is obtained being added in crystallization kettle and carries out crystallization reaction, the crystallization liquid solution after reaction Carry out the separation of liquid and crystal, wherein when crystallization Steam pressure control in 0~0.4Mpa, crystallize terminal point control 1.03~ 1.01。
2. APT according to claim 1 produces wastewater recycling method, which is characterized in that the step S3 alkali leaching is also Include: to heat up to the liquid after completion alkali leaching in alkali leaching kettle, when it is warming up to 90 DEG C, after keeping the temperature half an hour, passes through gas Liquid is discharged into underflow slot by liquid separating apparatus, and compressed air is pressed into underflow slot and is cooled down to underflow.
3. APT according to claim 2 produces wastewater recycling method, which is characterized in that the step S3 alkali leaching is also It include: that filters pressing is carried out when underflow temperature drops to 70 DEG C, filters pressing complete rear liquid or raffinate after the causticization, after adjusting filters pressing Filtrate in tungstic acid concentration and pH value, keep it in 110-120g/L, PH=10~14.
4. APT according to claim 3 produces wastewater recycling method, which is characterized in that the step S3 alkali leaching is also It include: that secondary filter is carried out to the filtrate after filters pressing, filtered refined filtration liquid, which enters in the step S4, carries out extraction reaction.
5. APT according to claim 1 produces wastewater recycling method, which is characterized in that also wrapped in the step S6 It includes molybdenum removal process: the vulcanization strip liquor after standing is added except molybdenum device is carried out except molybdenum, it is described except molybdenum device includes accurate mistake The lower part inlet of filter, the discharge port of the accurate filter and packed moving bed connects, the vulcanization strip liquor with 1~ 2m3The flow of/h is obtained after the Special Resin in packed moving bed is except molybdenum except liquid after molybdenum, through on packed moving bed with uplink mode The outflow of portion's liquid outlet.
6. APT according to claim 5 produces wastewater recycling method, which is characterized in that the packed moving bed Top is provided with top and is provided with resin inlet, and lower part 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, and is then delivered in heavy molybdenum reaction kettle, use is dense Sulfuric acid adjusts its PH=1~3 in heavy molybdenum reaction kettle, precipitates molybdenum, and after filters pressing, molybdenum enters progress molybdenum recycling in residue, obtains To seasoning liquid.
7. APT according to claim 6 produces wastewater recycling method, which is characterized in that also wrapped in the step S6 Include tungsten removal process: the seasoning liquid is after secondary filter, after carbon column oil removing, carries out tungsten using ion exchange column Recycling, the tungstenic peak liquid for then desorbing acquisition are uniformly mixed with the feed liquid in the step S3.
8. APT according to claim 7 produces wastewater recycling method, which is characterized in that also wrapped in the step S7 Include ammonia recovering process: after ammonia, the vapor released when evaporative crystallization in the crystallization kettle is recovered, production ammonium hydroxide is used to Stripping agent is prepared, into being stripped in the step S5.
9. APT according to claim 8 produces wastewater recycling method, which is characterized in that the negative molybdenum resin is through solving The tail washings generated in tail washings caused by inhaling and tungsten removal process is discharged into wastewater disposal basin, is evaporated by triple effect evaporator；It steams Steam pressure control is in 0.1~0.2Mpa when hair, and vacuum degree control is in -0.03~-0.08Mpa.
CN201610985109.4A 2016-10-25 2016-10-25 A kind of APT production wastewater recycling method Active CN106430787B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610985109.4A CN106430787B (en) 2016-10-25 2016-10-25 A kind of APT production wastewater recycling method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610985109.4A CN106430787B (en) 2016-10-25 2016-10-25 A kind of APT production wastewater recycling method

Publications (2)

Publication Number Publication Date
CN106430787A CN106430787A (en) 2017-02-22
CN106430787B true CN106430787B (en) 2019-09-06

Family

ID=58208122

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610985109.4A Active CN106430787B (en) 2016-10-25 2016-10-25 A kind of APT production wastewater recycling method

Country Status (1)

Country Link
CN (1) CN106430787B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
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
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
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
a novel process for tungsten hydrometallurgybased on direct solvent extraction in alkaline medium;Guiqing Zhang,etc;《Hydrometallurgy》;20160414;第233-237页

Also Published As

Publication number Publication date
CN106430787A (en) 2017-02-22

Similar Documents

Publication Publication Date Title
CN106430787B (en) A kind of APT production wastewater recycling method
CN100558633C (en) The method for preparing PHOSPHORIC ACID TECH.GRADE, food grade phosphoric acid and industrial monoammonium phosphate with phosphoric acid by wet process
CN102145912A (en) Process for preparing calcium chloride solution by utilizing ammonia soda filtration mother liquor
CN103553138A (en) Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water
CN206494958U (en) Iron removal system for zinc hydrometallurgy
CN202016881U (en) System for producing soda ash and ammonium sulfate
CN106744721A (en) The recovery separation method and application of sulfuric acid and dissolubility titanium in titanium white waste acid
CN104495927A (en) Method for preparing vanadium pentoxide
CN105084370A (en) Slag slurry treatment method and treatment apparatus in high-pressure low-temperature hydrogenation process
CN103288286B (en) Catalytic oxidation treatment method for desulfurized waste liquid
CN104451152A (en) Continuous recovery device and continuous recovery process of vanadium, molybdenum and titanium in SCR (selective catalytic reduction) waste catalyst
CN207376099U (en) A kind of dead catalyst utilization system
CN101767802A (en) Method for recycling ammonium sulphate from waste mineral slag of electrolytic manganese metal
CN101108815A (en) Method of recycling precipitating agent in production of L-leueine
CN101857212B (en) Method for preparing food-grade monoammonium phosphate from wet-process phosphoric acid
CN87103373A (en) Reclaim the method for iron oxide red and sulphur ammonium in the spent pickle liquor
CN108569812A (en) A kind of processing system and processing method of the waste water containing low-concentration sulfuric acid
US7387770B2 (en) Method for ferric sulfate manufacturing
CN106967114A (en) A kind of phosethyl-Al waste water reclaiming comprehensive processing method and system
CN103818883A (en) Step-by-step separation system and method for extracting salts from coking HPF desulfurizing solution by aqueous phase method
CN102531027A (en) Method for preparing heavy basic copper carbonate
CN107686193A (en) A kind of method for handling high-concentration sulfuric acid ammonium waste water
CN207362315U (en) One kind is used for tungsten powder production line in waste hard grinding material
CN101880771A (en) Method for recovering magnesium from magnesium-contained waste liquid
CN106927506A (en) The processing method of ammonium uranyl tricarbonate crystalline mother solution

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

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

PE01 Entry into force of the registration of the contract for pledge of patent right