CN102199704B - Recycling use method of sodium chloride or sodium sulfate in hydrometallurgy - Google Patents
Recycling use method of sodium chloride or sodium sulfate in hydrometallurgy Download PDFInfo
- Publication number
- CN102199704B CN102199704B CN2011101265877A CN201110126587A CN102199704B CN 102199704 B CN102199704 B CN 102199704B CN 2011101265877 A CN2011101265877 A CN 2011101265877A CN 201110126587 A CN201110126587 A CN 201110126587A CN 102199704 B CN102199704 B CN 102199704B
- Authority
- CN
- China
- Prior art keywords
- sodium
- value
- hydrochloric acid
- sewage
- chlor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Abstract
The invention provides a recycling use method of sodium chloride or sodium sulfate in hydrometallurgy, which comprises the following processes: proportioning, sodium baking of raw materials, leaching of clinker, impurity removing of leachate, extraction/back extraction of fine filtrate, preparing of metal ammonium salt, deaminizing of supernatant and treating of wastewater. The recycling use method provided by the invention can realize infinite recycling use of sodium chloride or sodium sulfate added during the sodium salt baking process and production wastewater after separation in a production process in the field of hydrometallurgy, can save resources, realize environmental friendliness, save energy and lower production cost, and is applicable to the field of hydrometallurgy.
Description
Technical field
What the present invention proposed is the method that hydrometallurgy field reactant recycles, specifically the method that recycles in hydrometallurgy of sodium-chlor or sodium sulfate.
Background technology
The hydrometallurgy industry is extracted high purity metal salt or oxide compound from metalliferous mineral or industrial residue technical process is: the sodium roasting of metalliferous mineral or industrial residue → grog heating water leaching → leach liquor removal of impurities → extraction/reextraction (or ion-exchange) → quilt is carried the metal ion concentrated solution and is added ammonium salt → make metal ammonium salt.The additive of raw material sodium roasting has three kinds substantially: (1) calcined soda for industry, and (2) calcined soda for industry is main, adds a small amount of sodium sulfate, (3) calcined soda for industry is main, adds a small amount of sodium-chlor; Use hydrochloric acid, nitric acid or sulfuric acid when adjusting pH in the technique; The vitriol, nitrate or the muriate that add calcium, magnesium during the leach liquor removal of impurities; The parsing of ion exchange resin, regeneration sodium hydroxide and hydrochloric acid, sodium hydroxide and sulfuric acid, sodium hydroxide and nitric acid; With precipitation metal ammonium salts such as ammonium chloride, ammonium sulfate, ammoniacal liquor; The remaining liquid or the waste water that contain ammonium ion, sodium-chlor, yellow soda ash or the sodium sulfate of high density after supernatant liquor behind the precipitation metal ammonium salt and raffinate or the ion-exchange, because of complicated component, that the separating-purifying difficulty reaches greatly expense is high, directly enter natural water, waste resource, contaminate environment.Enterprise only pays close attention to the rate of recovery, production cost and the rate of profit of being carried metal in the whole Production Flow Chart; do not consider recycle and the environment protection of resource; as long as favourable to enterprise; various subsidiary material arbitrarily adopt except raw material, cause the disastrous effect that high energy consumption, pollutent high production, resource can't recycle.
Summary of the invention
For the supplementary additive-sodium-chlor that solves hydrometallurgy industry sodium roasting, the technical problem that the sodium sulfate infinite loop is used, present method proposes sodium-chlor or the sodium sulfate method that infinite loop is used in the hydrometallurgy Production Flow Chart.The method extracts/strips, produces metal ammonium salt, supernatant liquor deamination, sewage disposal operation process by batching, raw material sodium roasting, grog leaching, leach liquor removal of impurities, smart filtrate, solves the technical problem of sodium-chlor or sodium sulfate recycle in hydrometallurgy.
The scheme that technical solution problem of the present invention is taked is:
According to the raw material types of hydrometallurgy, selective chlorination sodium or sodium sulfate are as supplementary additive.Its technical process is:
1, batching: raw material and soda ash and sodium-chlor or sodium sulfate are measured batching in proportion, as raw material before the roasting;
2, raw material sodium roasting: the raw material for preparing is put in the roasting kiln, added thermal bake-out, obtain grog;
3, grog leaches: grog is put into leached in the container, then add the steam condensate that obtains from wastewater treatment by solid-to-liquid ratio, carry out hot water leaching, obtain leach liquor after the solid-liquid separation;
4, leach liquor removal of impurities: in leach liquor, add hydrochloric acid or sulfuric acid, adjust pH to set(ting)value, add again calcium, magnesium muriate or vitriol and the aluminate of set amount after, precipitation is removed impurity, obtains removal of impurities essence filtrate;
5, smart filtrate extraction/strip: add hydrochloric acid or the sulfuric acid of set amount in the smart filtrate, adjust pH value, by comparing with in the pump input extractor of setting, fully being mixed with extraction agent extracts, and formation contains the richness of setting concentration and carries organic phase and raffinate; With pump richness is carried organic phase input stripper, when stirring, add aqueous sodium hydroxide solution or ammonia soln in the set amount ratio, generate to contain and set the aqueous solution and the extraction agent that concentration is extracted metal ion, extraction agent recycles;
6, produce the metal ammonium salt: will set the aqueous solution input metal ammonium salt precipitation device that concentration is extracted metal ion with pump, adjust the pH value with hydrochloric acid or sulfuric acid, under design temperature, the ammonium chloride or ammonium sulfate, ammoniacal liquor, hydrochloric acid or the sulfuric acid precipitation agent that add preset proportion in the precipitation reactor, after chemical reaction, produce metal ammonium salt precipitation, make the metal ammonium product salt that quality meets national standard after the solid-liquid separation, produce simultaneously the supernatant liquor that contains ammonium and muriate or vitriol;
7, supernatant liquor deamination: the sodium hydroxide that adds set amount in the supernatant liquor behind the separating metal ammonium salt, supernatant liquor is transported to the deammoniation tower top with pump, deamination under the condition of heating, containing the ammoniacal liquor steam is overflowed by cat head, through cooling, contain and obtain the ammoniacal liquor product that quality meets national standard behind the ammonia vapor condensation, the sewage behind the deamination is discharged for sewage disposal at the bottom of by tower;
Sewage disposal:
8.1, sewage mixes: the sewage behind the deamination and raffinate are injected in the mixing tank mix, form combined sewage;
8.2, sewage evaporation: combined sewage is input in the multiple-effect evaporator, and heating evaporation forms water of condensation behind the water vapor condensation, is back to use to produce each operation and recycle, and obtains simultaneously the isolate of crystallization, and main component is sodium-chlor or sodium sulfate;
8.3, crystallisate is dry: will evaporate the crystallisate that produces and separate drying, obtain sodium-chlor or sodium sulfate product, as the raw material of preparing burden.
Positively effect: sodium-chlor or sodium sulfate and factory effluent infinite loop use in Production Flow Chart after separating that the inventive method can make the hydrometallurgy field drop at the sodium roasting burden process.Have economize on resources, environmental protection, the energy-conservation and characteristics that reduce production costs.Suit to use in the hydrometallurgy field.
Description of drawings
Fig. 1 is that sodium-chlor of the present invention recycles procedure chart
Fig. 2 is that sodium sulfate of the present invention recycles procedure chart
Among the figure, 1. batching, 2. raw material sodium roasting, 3. grog leaches, 4. leach liquor removal of impurities, the metal ammonium salt is 6. produced in 5. smart filtrate extraction/strip, 7. supernatant liquor deamination, 8.1. sewage mixes, the 8.2. sewage evaporation, the 8.3. crystallisate separates dry.
Embodiment
According to illustrated in figures 1 and 2, the inventive method Production Flow Chart is:
1, batching: raw material and soda ash and sodium-chlor or sodium sulfate are measured batching in proportion, as raw material before the roasting;
2, raw material sodium roasting: the raw material for preparing is put in the roasting kiln, added thermal bake-out, obtain grog;
3, grog leaches: grog is put into leached in the container, then add the steam condensate that obtains from wastewater treatment by solid-to-liquid ratio, carry out hot water leaching, obtain leach liquor after the solid-liquid separation;
4, leach liquor removal of impurities: in leach liquor, add hydrochloric acid, sulfuric acid, adjust pH value to the pH value of setting, add again calcium, magnesium muriate or vitriol and the aluminate of set amount after, precipitation is removed impurity, the smart filtrate of acquisition removal of impurities;
5, smart filtrate extraction/strip: the hydrochloric acid or the sulfuric acid that add set amount in the smart filtrate, adjust the pH value, by suitable comparing with in the pump input extractor, fully be mixed with extraction agent and extract, formation contains the richness of setting concentration and carries organic phase and raffinate, with pump richness is carried organic phase input stripper, when stirring, add aqueous sodium hydroxide solution or ammonia soln in the set amount ratio, generation contains sets the aqueous solution and the extraction agent that concentration is extracted metal ion, and extraction agent recycles;
6, produce the metal ammonium salt: the setting concentration that will obtain after will stripping with pump is extracted the aqueous solution input metal ammonium salt precipitation device of metal ion, adjust the pH value with hydrochloric acid or sulfuric acid, under design temperature, add the ammonium chloride of set amount or ammonium sulfate, ammoniacal liquor hydrochloric acid, sulfuric acid precipitation agent in the precipitation reactor, after chemical reaction, produce metal ammonium salt precipitation, make the metal ammonium product salt that quality meets national standard after the solid-liquid separation, produce simultaneously the supernatant liquor that contains ammonium and muriate or vitriol;
7, supernatant liquor deamination: the sodium hydroxide that adds set amount in the supernatant liquor behind the separating metal ammonium salt, supernatant liquor is transported to the deammoniation tower top with pump, deamination under the condition of heating, obtain the ammoniacal liquor product that quality meets national standard after containing the ammonia vapor condensation, containing ammonia steam is overflowed by cat head, sewage is discharged at the bottom of by tower behind the deamination, supplies with sewage disposal;
Sewage disposal:
8.1, sewage mixes: the sewage behind the deamination and raffinate are injected in the mixing tank mix, form combined sewage;
8.2, sewage evaporation: combined sewage is input in the multiple-effect evaporator, and heating evaporation forms water of condensation behind the water vapor condensation, is back to use to produce each operation and recycle, and obtains simultaneously the isolate of crystallization, and main component is sodium-chlor or sodium sulfate;
8.3, crystallisate is dry: will evaporate the crystallisate that produces and separate drying, obtain sodium-chlor or sodium sulfate product, as the raw material of preparing burden.
In the full scale production flow process, can access metal ammonium salt, ammoniacal liquor and sodium-chlor or sodium sulfate product, also obtain simultaneously steam condensate.Steam condensate is back to use produces each operation infinite loop use, and sodium-chlor or sodium sulfate product reuse burden process as raw material.The infinite loop utilization of water and the infinite loop utilization of sodium-chlor or sodium sulfate have been realized.
The inventive method specific operation process
Process choice: the production process route of present method is with basic identical take calcined soda for industry as the operational path of sodium roasting additive, standard the use of the supplementary additive of sodium roasting, pH adjusting agent, leach liquor cleaner and metal ammonium salt precipitation agent, increased sewage treatment process.Take calcined soda for industry as sodium roasting master additive the time, it is the supplementary additive of sodium roasting that present method is recommended sodium sulfate or sodium-chlor, selective chlorination sodium be supplementary additive be called the chloride process system, select sodium sulfate be supplementary additive be called the sulfate process system.
The sodium roasting of raw material: (1) chloride process system, can fully react 1.0～1.3 times of required soda ash theoretical value as 100% with soda ash in the raw material of metalliferous mineral or industrial residue, the calcined soda for industry of adding 60～95% when sodium roasting is prepared burden, remainder adds the salt of (5～40%) * 110% ÷ sodium-chlor %, the rear input rotary kiln that fully is mixed carries out sodium roasting, 830～950 ℃ of temperature controls, reacted 4～6 hours, and carried metal in the grog and be converted into this metal soluble sodium salt rate and reach more than 96.0%.(2) sulfate process system, can fully react 1.0～1.3 times of required soda ash theoretical value as 100% with soda ash in the raw material of metalliferous mineral or industrial residue, the calcined soda for industry of adding 60～95% when sodium roasting is prepared burden, remainder adds the sodium sulfate of (5～40%) * 134% ÷ sodium sulfate %, the rear input rotary kiln that fully is mixed carries out sodium roasting, 860～980 ℃ of temperature controls, reacted 4～6 hours, and carried metal in the grog and be converted into this metal soluble sodium salt rate and reach more than 96.5%.
Grog leaches: solid-to-liquid ratio=1: 2～3; The steam condensate that grog produces after with production wastewater treatment soaked under 85 ± 5 ℃ 40～60 minutes, carried out solid-liquid separation with filter, and the leach liquor that contains the soluble metal sodium salt enters the removal of impurities operation.
Leach liquor removal of impurities: process choice chloride process system, muriate and the aluminates such as cleaner selective chlorination calcium, magnesium chloride; Adjust the leach liquor pH value with hydrochloric acid or sodium hydroxide; Impurity removal process control index is by traditional technology control; Completely reacted slip carries out solid-liquid separation with filter first, uses the accurate filter essence filter of aperture＜3u again, and smart filtrate enters next procedure.Process choice sulfate process system, cleaner is selected vitriol and the aluminates such as calcium sulfate, sal epsom; Adjust pH of leaching solution with sulfuric acid or sodium hydroxide; Impurity removal process control index is by traditional technology control; The completely reacted slip of removal of impurities carries out solid-liquid separation with filter first, uses the accurate filter essence filter of aperture＜3u again, and smart filtrate enters next procedure.
The processing of essence filtrate:
Essence filtrate contains and is extracted concentration of metal ions and reaches this precipitation by metallic ion processing requirement, produces the metal ammonium salt.
Essence filtrate contains and is extracted concentration of metal ions less than this precipitation by metallic ion processing requirement, (1) adopts traditional extraction/anti-extraction process, make and be extracted concentration of metal ions greater than the minimum concentration of this precipitation by metallic ion, this strip liquor is called rich sodium Metal 99.5 salts solution, and raffinate is transported to sewage disposal; Process choice chloride process system, adjust pH with hydrochloric acid or sodium hydroxide; Process choice sulfate process system, adjust pH with sulfuric acid or sodium hydroxide.(2) also can adopt traditional ion exchange process to make and be carried the minimum concentration of concentration of metal ions greater than this ion precipitation, this desorbed solution is called rich sodium Metal 99.5 salts solution, and the remaining liquid after the ion-exchange is transported to sewage disposal; Process choice chloride process system, use sodium hydroxide and resolving hydrochloric acid, regenerating resin; Process choice sulfate process system, use the parsing of sodium hydroxide and sulfuric acid, regenerating resin.
Carried producing of metal ammonium salt: it is a lot of to be put forward metal ammonium salt kind, and existing multiple from being put forward the successful technique of producing this metal ammonium salt the rich sodium Metal 99.5 salts solution both at home and abroad, the present invention agrees that manufacturing enterprise adopts original production process.Present method requires: process choice chloride process system, adjust the pH value of rich sodium Metal 99.5 salts solution with hydrochloric acid or sodium hydroxide, make precipitation agent with ammonium chloride or hydrochloric acid; Process choice sulfate process system, adjust the pH value of rich sodium Metal 99.5 salts solution with sulfuric acid or sodium hydroxide, make precipitation agent with ammonium sulfate or sulfuric acid; Washing metal ammonium salt needs with softening water or ammonia soln.Supernatant liquor behind the precipitation metal ammonium salt is transported to sewage disposal.
Sewage disposal:
Production Flow Chart produces two kinds of sewage, namely extracts supernatant liquor behind the metal ammonium salt and the remaining liquid after raffinate or the ion-exchange.The main component of supernatant liquor is sodium ion, chlorion, ammonium ion or sodium ion, sulfate ion, ammonium ion; The main component of raffinate (or the remaining liquid after the ion-exchange) is sodium ion, chlorion or sodium ion, sulfate ion.
First supernatant liquor is equipped with an amount of sodium hydroxide, under the condition of abundant mixing, transports to special-purpose denitrification column top with pump, the saturated vapor of 0.2～0.4MPa is passed into by the bottom of tower.Under 100～120 ℃ condition, feed liquid by cat head through multistage tower tray and filler stream at the bottom of the tower, finish NH in this process feed liquid
4 ++ OH
-1=NH
3↑+H
2The reaction of O.The new ammonia that produces is overflowed by the cat head pipeline opening, cools through surface condenser, and ammonia is dissolved in the water vapour of condensation and makes GB ammoniacal liquor product.Deamination liquid is discharged at the bottom of by tower, and main component sodium ion, chlorion or sodium ion, sulfate ion are transported to sewage disposal workshop section with pump.The specification of special-purpose deammoniation tower is determined according to ammonia nitrogen concentration and the generation of every day of supernatant liquor.
Remaining liquid after deamination liquid and raffinate or the ion-exchange is transported to the sewage mixing tank, transport to again multiple-effect evaporator after fully being mixed and carry out evaporative crystallization, separate and the drying machine drying through whizzer again, product is colourless sodium-chlor or anhydrous sodium sulphate, return the sodium roasting burden process and recycle, refer to the input amount of raw material sodium roasting batching.The evaporation condensed water of sewage all returns production system and recycles.
1. process choice chloride process system.The vanadium slag that produces take smelting iron and steel enterprise is as raw material, and sodium roasting is take calcined soda for industry as main additive, and salt is supplementary additive.
2. the sodium roasting of raw material: take the elements such as Vanadium in Vanadium Residue and the abundant reaction theory value of calcined soda for industry 1.25 times as 100%, the calcined soda for industry of adding 85% when sodium roasting is prepared burden, the salt that adds 15% * 110% ÷ sodium-chlor %, the rear input rotary kiln that fully is mixed carries out sodium roasting, temperature is controlled at 900 ± 30 ℃, reacted 3.5 hours, vanadium is converted into soluble vanadium and reaches more than 96.5% in the grog, supplies with and leaches operation.
3. grog leaches: the steam condensate that grog and sewage disposal produce is 1: 2～3 to drop into batch extractors in mass ratio, and constant temperature is 45 minutes under the condition of 85 ± 5 ℃ and stirring, with the slag stock pump slip is inputted flame filter press afterwards and carries out solid-liquid separation.Liquid is that the leach liquor that contains vanadium is supplied with the removal of impurities operation, and the material slag is delivered to the slag field after three countercurrent washings.
4. leach liquor removal of impurities: make cleaner with calcium chloride and sodium metaaluminate, with the pH value of hydrochloride adjusted solution, temperature of reaction, pH and reaction times are by the traditional technology operation.Completely reacted feed liquid is carried out solid-liquid separation with pump input flame filter press, and filtrate is the millipore filter essence filter of via hole diameter＜2.5u again, smart filtrate input extraction process, and the material slag send the slag field after three countercurrent washings.
5. the extraction of smart filtrate/reextraction: adjust smart filtrate pH value to set(ting)value with hydrochloric acid before the extraction, use the pH value of hydrochloric acid control solution in the extraction; Reverse-extraction agent is prepared with sodium hydroxide.The selection of the progression of extraction/reextraction, pH value, temperature, extraction agent, the concentration of reverse-extraction agent and reaction times are by the traditional technology operation.Vanadium concentration V=35～48g/L in the extraction/rich vanadium aqueous solution that produces of stripping transports to ammonium meta-vanadate or ammonium poly-vanadate is produced operation, and raffinate is transported to the sewage disposal operation.
6. producing of ammonium meta-vanadate or ammonium poly-vanadate: the pH value of adjusting the rich vanadium aqueous solution with hydrochloric acid is made precipitation agent to processing requirement with ammonium chloride, makes washing composition with ammonia soln.The concentration of producing pH value, temperature, reaction times, ammonium chloride input amount and the ammoniacal liquor of ammonium meta-vanadate or ammonium poly-vanadate solution operates by traditional technology, the ammonium meta-vanadate of production or ammonium poly-vanadate examination and test of products packing warehouse-in.The precipitation supernatant liquor is transported to the sewage disposal operation with pump.
7. supernatant liquor deamination:
The precipitation supernatant liquor is joined an amount of sodium hydroxide, after fully being mixed, transport to efficient deammoniation tower top with pump, 0.2 the saturated steam of～0.4MPa is passed into by the bottom of tower, under 103～110 ℃ condition, feed liquid by cat head through multistage tower tray and filler stream at the bottom of the tower, in steam and the abundant contact process of feed liquid adverse current, finish NH
4 ++ OH
-=NH
3↑+H
2The reaction of O.The new ammonia that produces is overflowed by the cat head pipeline opening, cools through surface condenser, and ammonia is dissolved in the water vapour of condensation and makes GB ammoniacal liquor product.Deamination liquid is discharged at the bottom of by tower, and main component is sodium ion and chlorion, and ammonia concentration is transported to the sewage disposal operation less than 80PPm with pump.The specification of special-purpose deammoniation tower is determined according to the ammonia nitrogen concentration of precipitation supernatant liquor and the volume that produces every day.
Sewage disposal:
Transport to triple-effect evaporator after deamination liquid and raffinate be mixed and carry out evaporative crystallization, separate and the drying machine drying through whizzer again, product is colourless sodium chloride crystal, returns the sodium roasting burden process and recycles, the sodium-chlor amount that drops into when referring to raw material sodium roasting batching.The evaporation condensed water of sewage all returns production system and recycles.
1. process choice: sulfate process system.The vanadium slag that produces take Iron And Steel Industry is as raw material, and take calcined soda for industry as main additive, sodium sulfate is supplementary additive during sodium roasting.
2. the sodium roasting of raw material: take the elements such as Vanadium in Vanadium Residue can with 1.15 times of the abundant reaction theory value of calcined soda for industry as 100%, the calcined soda for industry of adding 65% when sodium roasting is prepared burden, the sodium sulfate that adds 35% * 134% ÷ sodium sulfate %, the rear input rotary kiln that fully is mixed carries out sodium roasting, temperature is controlled at 890 ± 30 ℃, reacted 4 hours, vanadium is converted into soluble vanadium and reaches more than 96.6% in the grog, supplies with and leaches operation.
3. grog leaches: the steam condensate 1: 2 in mass ratio～2.8 that grog and sewage disposal produce drops into batch extractor, constant temperature is 40～50 minutes under 80 ± 5 ℃ and the condition that stirs, with the slag stock pump slip input flame filter press is carried out solid-liquid separation afterwards, liquid is supplied with the removal of impurities operation for containing vanadium leachate, and the material slag send the slag field after three countercurrent washings.
4. leach liquor removal of impurities: make cleaner with sal epsom and sodium aluminate, adjust pH with sulfuric acid, the temperature of reaction, time and pH value are by the traditional technology operation.Completely reacted feed liquid is carried out solid-liquid separation with pump input flame filter press, and filtrate is the millipore filter essence filter of via hole diameter＜2.5u again, smart filtrate input ion-exchange process, and the material slag send the slag field after three countercurrent washings.
5. ion-exchange: with sulfuric acid the pH value of smart filtrate is adjusted to processing requirement, inputs ion-exchanger with pump, after resin absorption is saturated, resolve resin with the sodium hydroxide solution of setting concentration, again with the sulphuric acid soln regenerating resin of setting concentration.The indexs such as the selection of the required resin of ion-exchange, smart filtrate pH value, concentration of sodium hydroxide solution, sulphuric acid soln concentration are by the traditional technology operation.The rich vanadium aqueous solution V=30～40g/L that resolves transports to ammonium meta-vanadate or ammonium poly-vanadate is produced operation; Remaining liquid after the ion-exchange is transported to the sewage disposal operation.
6. ammonium meta-vanadate or ammonium poly-vanadate are produced: the pH value of adjusting the rich vanadium aqueous solution with sulfuric acid or sodium hydroxide is made precipitation agent to processing requirement with ammonium sulfate, makes washing composition with ammonia soln.PH value, temperature, reaction times, the input amount of ammonium sulfate and the concentration of ammoniacal liquor of producing ammonium meta-vanadate or ammonium poly-vanadate solution operate by traditional technology.The ammonium meta-vanadate of producing or ammonium poly-vanadate examination and test of products packing warehouse-in, the precipitation supernatant liquor is transported to the sewage disposal operation.
7. supernatant liquor deamination: operating process is undertaken by the step of embodiment 1.
Sewage disposal is undertaken by the step of embodiment 1.
1. process choice: sulfate process system.Take molybdenum-contained waste catalyst as raw material, take calcined soda for industry as main additive, sodium sulfate is supplementary additive during sodium roasting.
The sodium roasting of 2 raw materials: in the spent catalyst 1.3 times of the element such as molybdenum and the abundant reaction theory value of calcined soda for industry as 100%, when sodium roasting is prepared burden, add 75% calcined soda for industry, add 25% * 134% ÷ Na
2SO
4The sodium sulfate of %, the rear input rotary kiln that fully is mixed carries out sodium roasting, and temperature is controlled at 880 ± 20 ℃, and in 4 hours reaction times, molybdenum is converted into soluble molybdenum and reaches more than 96% in the grog, and grog is supplied with and is leached operation.
3. grog leaches: grog drops into batch extractors with the steam condensate 1: 2 in mass ratio～2.5 that sewage disposal produces, and constant temperature is 45 minutes under the condition of 85 ± 5 ℃ and stirring.With pump slip input flame filter press is carried out solid-liquid separation afterwards, filtrate is supplied with the removal of impurities operation for containing the molybdenum leach liquor; The material slag send the slag field after three countercurrent washings.
4. leach liquor removal of impurities: make cleaner with calcium sulfate and sodium metaaluminate, adjust the pH value of solution with sulfuric acid, the temperature of removal of impurities, pH value and time are by the traditional technology operation.Completely reacted feed liquid is carried out solid-liquid separation with pump input flame filter press, and filtrate is the millipore filter essence filter of via hole diameter＜2.5u again, and smart filtrate input extracts workshop section, and the material slag send the slag field through three countercurrent washings.
5. the extraction of smart filtrate/reextraction: adjust the pH value of smart filtrate before the extraction with sulfuric acid, with the pH value of sulfuric acid control solution, reverse-extraction agent is prepared with ammoniacal liquor in the extraction.The concentration of the progression of extraction/reextraction, pH value, temperature, solvent selection, reverse-extraction agent and reaction times are by the traditional technology operation.Mo=60～150g/L in the rich molybdenum aqueous solution of extraction/reextraction transports to ammonium molybdate and produces operation, and raffinate is transported to the sewage disposal operation.
6. producing of ammonium tetramolybdate: with pump the rich molybdenum aqueous solution is transported to reactor, sulfuric acid is made precipitation agent, makes washing composition with ammoniacal liquor.The concentration of time, temperature, pH value and the ammoniacal liquor of reaction is by the traditional technology operation, and completely reacted slip separates the ammonium tetramolybdate examination and test of products that produces with whizzer and packs warehouse-in, and heavy molybdenum supernatant liquor is transported to sewage disposal workshop section.
7. supernatant liquor deamination: operating process is undertaken by the step of embodiment 1.
Sewage disposal is undertaken by the step of embodiment 1.
The supplementary additive sodium sulfate that the raw material sodium roasting uses or sodium-chlor are the general industry product, wherein the content of sodium sulfate or sodium-chlor all＞85%, all the other compositions meet national standard, moisture can exceed standard.The sulfuric acid that uses in the Production Flow Chart, hydrochloric acid and sodium hydroxide foreign matter content meet national standard, and the content of its sulfuric acid, hydrochloric acid and sodium hydroxide satisfies need of production and gets final product.
Contain the ammonia nitrogen factory effluent through ammonia nitrogen removal preparing ammonia fishery products, make waste water obtain rough purification; Again with raffinate or ion-exchange after remaining liquid be mixed after, dry through multiple-effect evaporator evaporative crystallization and drying machine, obtain anhydrous sodium sulphate or sodium-chlor product, returning the sodium roasting batching recycles, the input amount that refers to the sodium roasting batching, factory effluent is purified, becomes the water purification of recycling water temperature＞90 ℃.Present method can make ammonium ion, sodium sulfate or the sodium sulphite in the factory effluent realize resource utilization, makes it simultaneously to purify and recycling; Anhydrous sodium sulphate, sodium-chlor can infinite loop use in Production Flow Chart, refer to the input amount of sodium roasting batching, save a large amount of calcined soda for industry, reduce production costs.The characteristics that have significantly energy-conservation, consumption reduction, reduction of discharging, synergy and develop a circular economy.
Claims (1)
1. the method that recycles in hydrometallurgy of sodium-chlor or sodium sulfate is characterized in that:
1), batching: raw material and soda ash and sodium-chlor or sodium sulfate are measured batching in proportion, as raw material before the roasting;
2), raw material sodium roasting: the raw material for preparing is put in the roasting kiln, added thermal bake-out, obtain grog;
3), grog leaches: grog is put into leached in the container, then add the steam condensate that obtains from wastewater treatment by solid-to-liquid ratio, carry out hot water leaching, obtain leach liquor after the solid-liquid separation;
4), the leach liquor removal of impurities: in leach liquor, add hydrochloric acid or sulfuric acid, adjust pH to set(ting)value, add again calcium, magnesium muriate or vitriol and the aluminate of set amount after, precipitation is removed impurity, obtains removal of impurities essence filtrate;
5), smart filtrate extraction/strip: the hydrochloric acid or the sulfuric acid that add set amount in the smart filtrate, adjust the pH value, by suitable comparing with in the pump input extractor, fully be mixed with extraction agent and extract, formation contains certain density richness and carries organic phase and extraction liquid, with pump richness is carried organic phase input stripper, when stirring, add aqueous sodium hydroxide solution or ammonia soln in the set amount ratio, generation contains the aqueous solution and the extraction agent that finite concentration is extracted metal ion, and extraction agent recycles;
6), produce the metal ammonium salt: set the aqueous solution input metal ammonium salt precipitation device that concentration is extracted metal ion after will stripping with pump, adjust the pH value with hydrochloric acid or sulfuric acid, under design temperature, in precipitation reactor, add ammonium chloride or ammonium sulfate, ammoniacal liquor, hydrochloric acid or sulfuric acid precipitation agent, after chemical reaction, produce metal ammonium salt precipitation, make the metal ammonium product salt that quality meets national standard after the solid-liquid separation washing, produce simultaneously the supernatant liquor that contains ammonium and muriate or vitriol;
7), supernatant liquor deamination: the sodium hydroxide that adds set amount in the supernatant liquor behind the separating metal ammonium salt, supernatant liquor is transported to the deammoniation tower top with pump, deamination under the condition of heating, containing ammonia steam is overflowed by cat head, obtain the ammoniacal liquor product that quality meets national standard after containing the ammonia vapor condensation, sewage behind the deamination is discharged at the bottom of by tower, enters sewage disposal;
Sewage disposal:
8.1), sewage mixes: the sewage behind the deamination and raffinate are injected in the mixing tank mix, form combined sewage;
8.2), sewage evaporation: combined sewage is input in the multiple-effect evaporator, and heating evaporation forms water of condensation behind the water vapor condensation, is back to use to produce each operation and recycle, and obtains simultaneously the isolate of crystallization, and main component is sodium-chlor or sodium sulfate;
8.3), crystallisate is dry: will evaporate the crystallisate that produces and separate drying, obtain sodium-chlor or sodium sulfate product, as the raw material of preparing burden;
When adopting sodium-chlor as supplementary additive, the cleaner that leach liquor removal of impurities process is used be with leach liquor in impurity form muriate and the aluminate of insoluble substance, what adjust the use of pH value is hydrochloric acid; What essence filtrate extraction process pH value was adjusted adding is hydrochloric acid; What produce the adding of metal ammonium salt process is ammonium chloride or ammoniacal liquor, and what adjust the use of pH value is hydrochloric acid, and what crystallisate separation drying process obtained is the sodium-chlor product;
When adopting sodium sulfate as supplementary additive, the cleaner that leach liquor removal of impurities process is used be with leach liquor in impurity form vitriol and the aluminate of insoluble substance, what adjust that pH value uses is sulfuric acid, smart filtrate extraction process pH value adjustment adding be sulfuric acid; What produce the adding of metal ammonium salt process is ammonium sulfate or ammoniacal liquor, and what adjust the use of pH value is hydrochloric acid; What crystallisate separation drying process obtained is the sodium sulfate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101265877A CN102199704B (en) | 2011-05-17 | 2011-05-17 | Recycling use method of sodium chloride or sodium sulfate in hydrometallurgy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101265877A CN102199704B (en) | 2011-05-17 | 2011-05-17 | Recycling use method of sodium chloride or sodium sulfate in hydrometallurgy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102199704A CN102199704A (en) | 2011-09-28 |
| CN102199704B true CN102199704B (en) | 2013-02-13 |
Family
ID=44660686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101265877A Active CN102199704B (en) | 2011-05-17 | 2011-05-17 | Recycling use method of sodium chloride or sodium sulfate in hydrometallurgy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102199704B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555953B (en) * | 2013-11-04 | 2015-11-11 | 青川县天运金属开发有限公司 | The whole circulation means of water in a kind of many metal hazards waste treatment process |
| CN103555932B (en) * | 2013-11-15 | 2015-07-22 | 紫金矿业集团股份有限公司 | Method for roasting molybdenum concentrate |
| FI126932B (en) * | 2014-09-02 | 2017-08-15 | Outotec Finland Oy | A method for removing sodium from chloride solutions |
| CN114455764B (en) * | 2022-02-10 | 2023-04-18 | 江苏强盛功能化学股份有限公司 | Treatment method of 2, 5-dimethyl-2, 5-bis (hydrogen peroxide) hexane washing wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1818098A (en) * | 2006-03-14 | 2006-08-16 | 吉林大学 | Comprehensive recovery for bullion ore with various metals |
| CN101503758A (en) * | 2009-03-25 | 2009-08-12 | 十堰绿华石煤研究所有限责任公司 | Vanadium ore oxidizing roast composite additive and vanadium ore calcination method |
| CN101570832A (en) * | 2009-06-03 | 2009-11-04 | 郴州雄风稀贵金属材料股份有限公司 | Process for recovering valuable metals in bismuth-containing material by selective chloride volatilizing method |
-
2011
- 2011-05-17 CN CN2011101265877A patent/CN102199704B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1818098A (en) * | 2006-03-14 | 2006-08-16 | 吉林大学 | Comprehensive recovery for bullion ore with various metals |
| CN101503758A (en) * | 2009-03-25 | 2009-08-12 | 十堰绿华石煤研究所有限责任公司 | Vanadium ore oxidizing roast composite additive and vanadium ore calcination method |
| CN101570832A (en) * | 2009-06-03 | 2009-11-04 | 郴州雄风稀贵金属材料股份有限公司 | Process for recovering valuable metals in bismuth-containing material by selective chloride volatilizing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102199704A (en) | 2011-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073061B (en) | Method for extracting tungsten and molybdenum in high molybdenum scheelite | |
| CN102531025B (en) | Method for treating rare earth ammonium chloride wastewater | |
| CN100489126C (en) | Method of reclaiming chemical industry products by using industrial slag containing vanadium, chromium, iron and phosphorous | |
| CN103922416B (en) | A kind of method of Separation and Recovery iron from red mud | |
| CN100558633C (en) | The method for preparing PHOSPHORIC ACID TECH.GRADE, food grade phosphoric acid and industrial monoammonium phosphate with phosphoric acid by wet process | |
| CN101679038B (en) | Phosphorus recovery | |
| CN101265524B (en) | Method for extracting V2O5 from stone coal | |
| CN101525189A (en) | Method for treating wastewater containing ammonia, vanadium, chrome and sodium sulfate | |
| CN113336246B (en) | Resource treatment method of waste salt | |
| CN102689930B (en) | Hydrochloric acid pickling waste liquid resource integrated utilization method for preparing iron oxide and ammonium sulfate | |
| WO2012163200A1 (en) | Method for separating rare earth from phosphorus ore | |
| CN101186284B (en) | Method for preparing phosphoric acid from phosphorus block ore by wet method and extracting rare earth from phosphorus block ore | |
| CA2707830A1 (en) | Liquid and solid effluent treatment process | |
| CN102491379A (en) | Method for preparing high-purity magnesium oxide with high boron salt lake brine | |
| CN102199704B (en) | Recycling use method of sodium chloride or sodium sulfate in hydrometallurgy | |
| Song et al. | Separation and recovery of lithium from Li3PO4 leaching liquor using solvent extraction with saponified D2EHPA | |
| US20240101440A1 (en) | Recovery Of Commercial Substances From Apatite Mineral | |
| CN105296753A (en) | Method for separating cobalt, nickel and magnesium from nickel oxide ore pickle liquor | |
| CN104411626A (en) | Production of ammonium phosphates | |
| CN104986909A (en) | Acidic ammonium salt vanadium precipitation waste water recycling method | |
| CN108728649A (en) | A kind of method of bone coal acid waste water recycling | |
| Li et al. | Wet process of phosphoric acid purification by solvent extraction using tri-n-butyl phosphate and cyclohexanol mixtures | |
| CN105731513B (en) | The method for producing rare earth oxide containing rare earth phosphate rock with regeneration phosphoric acid leaching | |
| CN108947012A (en) | A method of separating and recovering ammonia from ammonia nitrogen waste water | |
| JP5752794B2 (en) | Liquid effluent treatment and metal recovery methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 125017 Huludao province Liaoning City Nanpiao District Lo Hong Zhen Kao Shan Cun Qian pan Cun Xian (South Village Road) Patentee after: Liaoning Hong Kong Industrial Co., Ltd. Address before: 125017 Liaoning province Huludao city lianshanqu Lo Hong Xian Zhen Kao Shan Industrial Park Patentee before: Huludao Huihong Non-ferrous Metal Co., Ltd. |