CN108359813B - A kind of energy-saving and environment-friendly salt lake bittern proposes lithium technique - Google Patents
A kind of energy-saving and environment-friendly salt lake bittern proposes lithium technique Download PDFInfo
- Publication number
- CN108359813B CN108359813B CN201810135860.4A CN201810135860A CN108359813B CN 108359813 B CN108359813 B CN 108359813B CN 201810135860 A CN201810135860 A CN 201810135860A CN 108359813 B CN108359813 B CN 108359813B
- Authority
- CN
- China
- Prior art keywords
- lithium
- water
- nanofiltration
- brine
- extraction
- 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
Classifications
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- 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 discloses a kind of energy-saving and environment-friendly salt lake bitterns to propose lithium technique, comprising: high salinity brine strengthens nebulisation cycle concentration through tower heat and divides the atomization of salt device brine and forced evaporation, realizes high magnification numbe concentration and the salt reduction richness lithium of brine；Rich lithium brine is concentrated and divides salt demagging by multistage pressure nanofiltration, at the low lithium concentrate recirculation to tower concentration feed liquor of primary nanofiltration；Rich lithium nanofiltration produces water liquid-liquid extraction and mentions lithium, and raffinate water phase and extractant regeneration cleaning solution containing lithium are back to nanofiltration feed liquor, further recycle lithium；High lithium strip liquor evaporation recovery acid helps extraction agent for regenerating.The high lithium double salt of solid is obtained after evaporation deacidification, ethyl alcohol liquid-solid extraction will obtain lithium chloride ethyl alcohol and extract the volatilization of solution low temperature, and ethyl alcohol recycling obtains industrial grade methanol.The technique overall process energy-saving effect is significant, and the lithium rate of recovery is high, and production cost is low, safety and environmental protection.The extraction and production of lithium suitable for all kinds of high salinity, salt lake brine with high magnesium-lithium ratio.
Description
Technical field
The invention belongs to wet underwater welding rare precious metal technical field, in particular to a kind of energy-saving and environment-friendly salt lake bittern mentions lithium
Technique.
Background technique
Salt lake bittern is one of the main path of lithium resource exploitation.The main method that lithium is extracted from brine includes: precipitating
Method, absorption method, extraction, embrane method etc..However, the existing lithium technique that mentions has high production cost, energy consumption is high, and secondary pollution is serious
The defects of.Therefore, in the case where current country's height advocates the big policy tendency of environmental protection, developing the energy-saving and environment-friendly lithium technique that proposes is
The task of top priority.
Currently, brine, which is concentrated and separated the most common method, to be shone by salt pan beach, part monovalence is isolated using solar energy
Salt, or k-na salt content in brine is reduced by modes such as reduction vaporization.Patent CN101385904A provides a kind of concentration halogen
The method of water, mainly by pumping brine through pipeline to the atomising head being mounted on above concentraing pond, brine is through atomising head
It is contacted after ejection with air and reaches concentrated effect.But this method need to provide the operating environment of dry high temperature, concentrated effect vulnerable to
Weather influences, and a large amount of fugitive dust brings adverse effect to environment.Patent CN03108088.X discloses one kind and passes through nano filtering process
The method of enriching lithium from salt lake bittern, but traditional nanofiltration output is small, is not also suitable for high salinity brine, and this method
In, lithium primary nanofiltration concentrated water will be contained and do not recycled and direct emission, the loss and secondary pollution of lithium resource, patent are caused
CN101698488B provides a kind of method for preparing lithium carbonate from high Mg/Li ratio brine using extraction, but the method directly exists
Lye is added in highly acid strip aqueous and adjusts pH sinker, chemical agent usage amount is big, high production cost, and the technique does not mention
And help the recycling and reusing of extraction agent.The extraction that CN106521159A is provided mentions in lithium technique, is stripped using lye, adds regeneration of hydrochloric acid
In the method for co-extraction agent, lye is stripped a large amount of losses for easily leading to extractant, while the investment of external hydrochloric acid increases production again
Cost.CN102168183 provides a kind of method that low carbon chain organic compound extracts lithium in brine, however the method is using rudimentary
Alcohol directly containing lithium potassium, sodium, magnesium chlorination saline solution in, carry out liquid-liquid extraction.There is no consideration low carbon chains to have for the technique
The problems such as dissolubility of machine object in water, exists and mentions lithium limited efficacy, and organic phase is not easily recycled.
With a large amount of utilizations of lithium resource, rich lithium Brine resources are more short.It provides and a kind of solve existing salt lake bittern and mention
The energy-saving and environment-friendly salt lake bittern of high cost in lithium technique, high pollution and high energy consumption inefficiency problem, which proposes lithium technique, to be become at present originally
Field technical problem urgently to be resolved.
Summary of the invention
It is an object of the invention to for the prior art there are high production cost, energy consumption is high, secondary pollution is serious, lithium recycling
The low deficiency of rate, Gu provide a kind of forced circulation spray concentration desalination richness lithium+high pressure nanofiltration salt reduction demagging+liquid-liquid extraction richness lithium+
The group technology of lithium chloride is extracted in liquid extraction, comprising the following steps: high salinity brine strengthens nebulisation cycle concentration point through tower heat
Salt device, brine atomization and forced evaporation, lose sodium, potassium, the chloride of magnesium and sulfate because reaching supersaturation precipitation and crystallization
Water realizes high magnification numbe concentration and the salt reduction richness lithium of brine；Rich lithium brine is concentrated and divides salt demagging by multistage pressure nanofiltration, primary is received
It filters at low lithium concentrate recirculation to tower concentration feed liquor, reduces lithium loss；Rich lithium nanofiltration produces water liquid-liquid extraction and mentions lithium, the raffinate containing lithium
Water phase and extractant regeneration cleaning solution are back to nanofiltration feed liquor, further recycle lithium；High lithium strip liquor evaporation recovery acid is for again
Life helps extraction agent.The high lithium double salt of solid is obtained after evaporation deacidification, ethyl alcohol liquid-solid extraction will obtain lithium chloride ethyl alcohol and extract solution low temperature
Volatilization, ethyl alcohol reclaiming are reused, and industrial grade methanol is obtained.The technique overall process energy-saving effect is significant, and the lithium rate of recovery is high,
Production cost is low, safety and environmental protection.The extraction and production of lithium suitable for all kinds of high salinity, salt lake brine with high magnesium-lithium ratio.
The present invention is realized by following technical proposals.
A kind of energy-saving and environment-friendly salt lake bittern proposes lithium technique, comprising the following steps:
1) high salinity brine divides salt device circular treatment by tower heat reinforcing circulation spray concentration, makes in high salinity brine
Potassium, sodium, magnesium salts be precipitated with chloride and sulfuric acid salt loading mixed crystal, and obtain concentrated brine；Mixed crystal is through plate compression solid-liquid
Separation, respectively obtains intercrystalline water containing lithium and mixed salt；
2) through tower heat strengthen circulation spray concentration divide salt device treated concentrated brine with removed through plate compression it is solid
The intercrystalline water containing lithium of body impurity dilutes to obtain nanofiltration raw water through water, and enters multistage pressure nanofiltration system；
3) multistep treatment Jing Guo high pressure nanofiltration divides salt to remove magnesium ion, respectively obtains level-one nanofiltration production water and level-one is poor
Lithium concentrated water；The poor lithium concentrated water of level-one is rich in magnesium ion concentrated water, is back at tower feed liquid mouth feed liquor, continues desalination, recycles rich lithium；
4) level-one nanofiltration produces water and obtains multistage pressure nanofiltration production water through multistage pressure nanofiltration technique, through neutral carrier+trichlorine
Change iron, which helps, extracts lithium, respectively obtains the rich lithium organic phase of extraction and low lithium raffinate；In extracting rich lithium organic phase oil-water ratio according to
Mass ratio is that 10:1 adds the back extraction of 6-8M hydrochloric acid, respectively obtains rich lithium water phase and back extraction organic phase；
5) rich lithium water phase is steamed sour technique and respectively obtains compound chloride-based containing lithium and regenerate hydrochloric acid；Organic phase is stripped through regenerating work
Skill respectively obtains regenerating extracting agent and extractant regeneration cleaning solution, and regenerating extracting agent is back to use in the neutral carrier of step 4), follows
Ring uses；
6) extractant regeneration cleaning solution is mixed with the low lithium raffinate that step 3) obtains, and is added water to adjust pH > 3, is respectively obtained
Help extraction agent hydroxide sediment and mixed liquor containing lithium；Mixed liquor containing lithium is back to the high pressure nanofiltration system of step 2), recycles lithium
Ion；
7) the regeneration mixed in hydrochloric acid for helping extraction agent hydroxide and step 5) to obtain of separation obtains regeneration and helps extraction agent, and regeneration helps
Extraction agent is back to use energy-saving and emission-reduction in the ferric trichloride of step 4)；
8) liquid-solid extraction is carried out with ethyl alcohol containing lithium is compound chloride-based by what is obtained after step 5) evaporation deacidification, respectively obtain compound
Villaumite and rich lithium organic phase, rich lithium organic phase obtain extraction organic phase and high-purity lithium chloride products through low-temperature evaporation.
Further, in step 1), by salt lake ted produce salt, propose the corresponding process of boron after, lithium content between 0.15-2g/L,
Low lithium, Gao Mei, high salinity brine of the Mg/Li ratio (by quality ratio) between 50~1000:1, after heat strengthens circulation by spraying,
Brine volume reaches 5-10 times compared with raw water concentration.
Further, in step 2), nanofiltration raw water in the high pressure nanofiltration system, lithium content between 1.5-10g/L,
[Mg2+]=70-120g/L, Mg/Li ratio (by quality ratio) between 10-100:1, through heat strengthen circulation spray concentration brine and
Intercrystalline water mixes concentrated brine and dilutes 1-2 times, under 3-6MPa pressure, enters through nanofiltration membrane and produces water side, obtains nanofiltration and produces water
With nanofiltration concentrated water.
Further, in step 2), the multistage pressure nanofiltration produces water and refers to [Li+]=1-8g/L, [Mg2+]=5-30g/L, magnesium
Lithium ratio drops to 3-10:1, and brine volume is compared with 3-5 times of concentration of nanofiltration water inlet.
Further, in step 4), it is that 1.5:1 adds neutral carrier according to grease mass ratio, is added with iron lithium molar ratio for 2:1
Add ferric trichloride.
Further, the neutral carrier is that volume is 30-40% tributyl phosphate and 70-80% sulfonated kerosene is mixed with
Machine phase.
Further, in step 5), the regeneration hydrochloric acid refers to, nanofiltration is produced water mentions by extraction the strip liquor after lithium and lead to
Cross the rich lithium strip liquor middle and high concentration hydrochloric acid recycled after water vapour is evaporated+is dried under reduced pressure.
Further, in step 5), the extractant regeneration cleaning solution refers to: extraction organic phase mentions lithium through high concentrated acid back extraction
Afterwards, extractant must remove through low concentration alkali+neutral water cleaning and help extraction agent, obtain regenerating extracting agent and extractant regeneration cleaning solution；
The low concentration alkali is the sodium hydroxide solution of 1-3M.
Further, in step 6), in extractant regeneration cleaning aqueous residue, removing is helped outside extraction agent, still contains some
Lithium mixes the extractant regeneration cleaning solution containing lithium with raffinate raffinate, and water adjusting is added to make pH > 3, and extraction agent is helped to be hydrolyzed to hydroxide
Iron is precipitated, and the regeneration mixed in hydrochloric acid that iron hydroxide is obtained with step 3), which obtains regenerating, helps extraction agent-iron chloride, the iron chloride of recycling,
Step 3) can be back to use；Residue removes the mixed liquor containing lithium for helping extraction agent, continues to be back to nanofiltration charging mouth, recycle low concentration lithium from
Son.
The present invention correspondingly gives the tower heat reinforcing circulation spray concentration that the technique uses and divides salt device, including
Device noumenon, the former brine case being connected to device noumenon, described device ontology are circular tower type, and cavity internal upper part is equipped with spray dress
It sets, lower part is heat exchange type wind-guiding equipment, and bottom is equipped with concentrated brine collecting pit；Air blast is further connected in heat exchange type wind-guiding equipment
Device；Heat exchanger is set in former brine case, heat exchanger, ground-source heat pump host, heat exchange type wind-guiding equipment are made up of pipeline filled with cold
The closed system of matchmaker；Brine is transported to spray equipment by former brine case by brine pipeline and pump, carries out spray atomization.
The dissolubility difference of this technological basis lithium chloride, sodium chloride, potassium chloride in ethanol, passes through water vapour for strip liquor
Evaporation deacidification after being dried under reduced pressure, obtains approaching the villaumite of neutral solid lithium, sodium, potassium, magnesium, with ethyl alcohol liquid-solid extraction repeatedly.It will
Lithium chloride with other three kinds in ethanol the low villaumite solid of solubility separate, obtain the alcohol extraction liquid of lithium chloride.By chlorination
Lithium alcohol extraction liquid low-temperature evaporation obtains industrial grade methanol product, reuses after the recycling of extractant ethyl alcohol.The technique extractant
Ethyl alcohol boiling point is low, can evaporate under cryogenic, obtains solid and mentions lithium product, and can recycle ethyl alcohol.Raw materials for production consumption
Few, low energy consumption and without industrial discharge.
The present invention has the advantage that compared with other techniques
This technique is that forced circulation spray concentration desalination+high pressure nanofiltration point salt reduction demagging+liquid-liquid extraction+liquid-solid extraction mentions lithium
Group technology.High salinity brine first passes through forced-circulation evaporation and high power is concentrated, salt reduction richness lithium, compared with traditional handicraft, rapidly and efficiently,
Economization on land and time；The more traditional nanofiltration technique of this technique avoids high magnesium primary nanofiltration concentrated water of the direct emission containing lithium, passes through
After high pressure nanofiltration divides salt demagging, extraction series can be effectively reduced, improve extraction efficiency；Nanofiltration produces water after extracting, by high concentration
For sour strip liquor by the hydrochloric acid of water vapour evaporation recycling for helping extraction agent regeneration, save the cost simultaneously reduces environmental emission；It will evaporation
The neutral monovalent metal containing lithium after deacidification is compound chloride-based by ethyl alcohol liquid-solid extraction extraction lithium chloride, and product lithium chloride is easy to pure
Change, feed ethanol is easily recycled, energy conservation and environmental protection.
This technique is related to during energy-saving and environment-friendly salt lake bittern mentions lithium, and the extraction of lithium recycles, is high containing lithium in intercrystalline water
Pressure nanofiltration concentrated water and raffinate containing lithium, the reuse of extractant regeneration cleaning solution, hydrochloric acid and help extraction agent regeneration, liquid-solid extraction agent reuse
Etc. processes, embody energy-saving and environmental protection, emission reduction and reduce production cost the characteristics of.Especially suitable for high salinity, the salt of low lithium content
In lake bittern water, the extraction of lithium product.
Detailed description of the invention
Fig. 1 is that a kind of energy-saving and environment-friendly salt lake bittern provided by the invention mentions lithium process flow diagram.
Fig. 2 is that tower heat reinforcing circulation spray concentration provided by the invention divides salt schematic device.
Wherein: 1, former brine case；2, spray equipment；3, ground-source heat pump host；4, heat exchange type wind-guiding equipment；5, air blast fills
It sets；6, concentrated brine collecting pit, 7, sewage pump, 8, heat exchanger.
Specific embodiment
Below with reference to embodiment, the invention will be described in further detail, but be not intended as to invention do any restrictions according to
According to.
As shown in Figure 1, energy-saving and environment-friendly salt lake bittern of the invention proposes lithium technique, comprising the following steps:
1) salt lake is tedded after producing salt, proposing the corresponding process of boron, lithium content is between 0.15-2g/L, and Mg/Li ratio is (in mass ratio
Meter) low lithium, Gao Mei, high salinity brine between 50~1000:1, circulation spray concentration is strengthened by tower heat and divides salt device
Circular treatment, a large amount of magnesium carnallite complex salt crystal and the crystallization water for taking away quality by about one time, brine volume are reached compared with raw water concentration
5-10 times, and heat reinforcing can improve atomizer mouth salt solubility, avoid double salt from crystallizing at nozzle and block, to guarantee to steam
The continuous operation of hair process.The brine cycles of concentration of the technique is more traditional to be concentrated by evaporation significantly, and the energy consumption of subsequent technique is reduced
And production equipment.Lithium enrichment phase in brine answers multiple, and the intercrystalline water recycling in the double salt by being precipitated, to guarantee returning for lithium
Yield.The potassium in high salinity brine, sodium, magnesium salts is set to be precipitated with chloride and sulfuric acid salt loading mixed crystal, and obtain concentrated brine；
Mixed crystal is separated by solid-liquid separation through plate compression, respectively obtains intercrystalline water containing lithium and mixed salt.
2) through tower heat strengthen circulation spray concentration divide salt device treated concentrated brine with removed through plate compression it is solid
The intercrystalline water containing lithium of body impurity dilutes to obtain nanofiltration raw water through water, and lithium content is between 1.5-10g/L in nanofiltration raw water, [Mg2+]
=70-120g/L, Mg/Li ratio strengthen circulation spray concentration brine through heat and intercrystalline water mix concentrated brine between 10-100:1
1-2 times of dilution enters through nanofiltration membrane under 3-6MPa pressure and produces water side, obtains nanofiltration and produces water and nanofiltration concentrated water, and enters more
Grade high pressure nanofiltration system；Primary nanofiltration concentrated water of traditional nanofiltration technique direct emission containing lithium, causes lithium to lose, while generating secondary
Pollution.Primary low lithium nanofiltration concentrated water is continued to be back to tower feed liquid mouth feed liquor, remaining high lithium concentrated water at different levels is in nanofiltration by this technique
It flows back between system, further prevents the loss of lithium.
3) multistep treatment Jing Guo high pressure nanofiltration divides salt to remove magnesium ion, respectively obtains level-one nanofiltration production water and level-one is poor
Lithium concentrated water；The poor lithium concentrated water of level-one is rich in magnesium ion concentrated water, is back at tower feed liquid mouth feed liquor, continues desalination, recycles rich lithium；
4) level-one nanofiltration produces water and obtains multistage pressure nanofiltration production water through multistage pressure nanofiltration technique, and multistage pressure nanofiltration produces water
Refer to [Li+]=1-8g/L, [Mg2+]=5-30g/L, Mg/Li ratio drop to 3-10:1, and brine volume intakes compared with nanofiltration and 3-5 is concentrated
Times.Neutral carrier is added for 1.5:1 according to mass ratio according to oil-water ratio, is that 2:1 adds ferric trichloride with iron lithium molar ratio, in
Property carrier+ferric trichloride help and extract lithium, respectively obtain the rich lithium organic phase of extraction and low lithium raffinate；In extracting rich lithium organic phase
Oil-water ratio is that 10:1 adds the back extraction of 6-8M hydrochloric acid according to mass ratio, respectively obtains rich lithium water phase and back extraction organic phase；
Neutral carrier is the mixing organic phase that volume is 30-40% tributyl phosphate Yu 70-80% sulfonated kerosene.
5) rich lithium water phase steamed sour technique respectively obtain containing lithium is compound chloride-based and regeneration hydrochloric acid (regeneration hydrochloric acid refers to, will receive
Filter produces water and is mentioned in the rich lithium strip liquor recycled after the strip liquor after lithium is evaporated+is dried under reduced pressure by water vapour by extraction
Concentrated hydrochloric acid)；Back extraction organic phase through regeneration technology respectively obtains regenerating extracting agent and extractant regeneration cleaning solution, and (extractant is again
Raw cleaning solution refers to: after high concentrated acid back extraction mentions lithium, extractant must remove extraction organic phase through low concentration alkali+neutral water cleaning
Extraction agent is helped, regenerating extracting agent and extractant regeneration cleaning solution are obtained, wherein low concentration alkali is the sodium hydroxide solution of 1-3M), then
Raw extractant is back to use in the neutral carrier of step 4), is recycled；
6) in extractant regeneration cleaning aqueous residue, removing is helped outside extraction agent, still contains some lithium, by the extraction containing lithium
Agent regeneration washing liquid is mixed with raffinate raffinate, and water adjusting is added to make pH > 3, is respectively obtained and is helped extraction agent hydroxide sediment and containing lithium
Mixed liquor；Extraction agent is helped to be hydrolyzed to iron hydroxide precipitation, the regeneration mixed in hydrochloric acid that iron hydroxide is obtained with step 3) obtains regeneration and helps
Extract agent-iron chloride, the iron chloride of recycling can be back to use step 3)；Residue removes the mixed liquor containing lithium for helping extraction agent, continues to be back to
The high pressure nanofiltration system feed inlet of step 2) recycles low concentration lithium ion；
7) the regeneration mixed in hydrochloric acid for helping extraction agent hydroxide and step 5) to obtain of separation obtains regeneration and helps extraction agent, and regeneration helps
Extraction agent is back to use in the ferric trichloride of step 4)；
8) liquid-solid extraction is carried out with ethyl alcohol containing lithium is compound chloride-based by what is obtained after step 5) evaporation deacidification, respectively obtain compound
Villaumite and rich lithium organic phase, rich lithium organic phase obtain extraction organic phase and high-purity lithium chloride products through low-temperature evaporation.
The above are a kind of energy-saving and environment-friendly salt lake bitterns to mention lithium process program.
As shown in Fig. 2, the tower heat that present invention process use is given below, which strengthens circulation spray concentration, divides salt device, including
Device noumenon, the former brine case 1 being connected to device noumenon, device noumenon are circular tower type, and cavity internal upper part is equipped with spray equipment
2, lower part is heat exchange type wind-guiding equipment 4, and bottom is equipped with concentrated brine collecting pit 6；Further connection is roused in heat exchange type wind-guiding equipment 4
Wind apparatus 5；Heat exchanger 8 is set in former brine case 1, heat exchanger 8, ground-source heat pump host 3, heat exchange type wind-guiding equipment 4 pass through pipeline group
At the closed system filled with refrigerant；Brine is transported to spray equipment 2 by former brine case 1 by brine pipeline and sewage pump 7, carries out
Spray atomization.
Heat exchanger 8 in former brine case 1 is under the power effect of ground-source heat pump host 3, so that former brine cooling, part salt
Solid is precipitated, the heat of absorption is discharged in heat exchange type wind-guiding equipment 4 is concentrated by evaporation intercrystalline bittern water mist, the brine entrainment after concentration
Be precipitated solid salt grain be concentrated brine collecting pit 6 collection, achieve the purpose that part brine concentration divide salt.
Tower heat strengthens circulation spray concentration and divides salt device for round tower, and high salinity brine is sprayed from tower top with droplet form
Out.The wind that blower device generates absorbs the brine heat that earth source heat pump provides and heats up, and hot wind comes into full contact with droplet to be made wherein
Moisture rapid evaporation dehydration, after the sodium for causing partial solubility low, potassium, magnesium chloride and sulfate reach supersaturation, in tower bottom
Concentrated brine collecting pit accumulation divide salt, while collect concentration after high-concentrated brine.
The present invention is further illustrated below by specific embodiment.
Embodiment 1
Mechanical thickening equipment is that tower heat reinforcing circulation spray concentration divides salt device, and high pressure nanofiltration equipment includes membrane module,
High-pressure pump and production water pot.The composition of certain brine containing lithium: [Li+]=1.69g/L, [Mg2+]=114.73g/L, [Na+]=
25.20g/L [K+]=5.65g/L
1) tower heat reinforcing circulation spray concentration divides salt device richness lithium salt reduction
Lithium brine will be contained and divide salt device to carry out circulation concentration, brine volume concentration using tower heat reinforcing circulation spray concentration
5-6 times, potassium, sodium, magnesium salts are precipitated in the form of chloride solids in concentration process.
Strengthen spray concentration device circular treatment through heat, produces water after concentration: [Li+]=8.45g/L, [Mg2+]=
110.12g/L [Na+]=7.31g/L, [K+]=2.21g/L.
2) high pressure nanofiltration demagging
By after concentration production water and intercrystalline water filter through micro-filtration, water after filter dilutes one times of feeding first order high pressure nanofiltration,
Under 3Mpa pressure condition, concentrated brine is separated into first order concentrated water by nanofiltration membrane and the first order produces water.
The high pressure nanofiltration first order is produced into water and is sent into the nanofiltration of second level high pressure, under 3Mpa pressure condition, the first order produces water quilt
Nanofiltration membrane is separated into second level concentrated water and the second level produces water.Primary nanofiltration concentrated water is back to tower feed liquid mouth feed liquor, and second level is received
It filters at concentrate recirculation to upper level nanofiltration charging.Second level produces water volume and compares 2-3 times of volume concentration of high pressure nanofiltration charging brine.
After circulation concentration, second level high pressure nanofiltration processing, the high pressure nanofiltration second level produces the composition of water: [Li+]=6.34g/
L, [Mg2+]=19.75g/L, [Na+]=5.12g/L, [K+]=1.65g/L.
3) high pressure nanofiltration produces water extraction
Water lithium concentration is produced according to the high pressure nanofiltration third level, ferric trichloride is added with iron lithium molar ratio 2:1, by itself and organic extraction
System 70%TBP+30% sulfonated kerosene is taken to be extracted with 1: 1.5 volume ratio, extraction time 15min.
4) back extraction of organic phase
It is stripping agent with 8M hydrochloric acid, the volume ratio for controlling organic phase and stripping agent is 10: 1, and rich lithium organic phase is carried out four
Grade back extraction, single-stage back-extraction time are 10min.The total recovery of lithium is 92.3%.
5) extractant, help extraction agent, raffinate and extractant regeneration cleaning solution reuse
Strip aqueous is evaporated+is dried under reduced pressure by water vapour, obtains regeneration hydrochloric acid and the neutral monovalent metal containing lithium is compound
Villaumite.After reverse-extraction of high acid mentions lithium, extractant must remove through low concentration alkali+neutral water cleaning and help extraction agent oily phase extract liquor, obtain
Regenerating extracting agent.In extractant regeneration cleaning aqueous residue, removing is helped outside extraction agent, still containing the lithium of partial loss.Lithium will be contained
Extractant regeneration cleaning solution mixed with raffinate raffinate, add water adjust pH=3-5 between, help extraction agent be hydrolyzed to iron hydroxide analysis
Out.Residue removes the mixed liquor containing lithium for helping extraction agent, continues to be back to nanofiltration charging mouth, prevents lithium from losing, and improves the lithium rate of recovery.Hydrogen
Iron oxide recycles iron chloride, energy-saving and emission-reduction after the regeneration of hydrochloric acid that strip liquor steams.
6) liquid-solid extraction mentions lithium
The neutrality monovalent metal containing lithium that liquid-liquid extraction obtains is compound chloride-based to mention lithium by ethyl alcohol liquid-solid extraction, recrystallizes high
Purity lithium chloride products, extractant ethyl alcohol are recycled and are reused.
Embodiment 2
Mechanical thickening equipment is that tower heat reinforcing circulation spray concentration divides salt device, and high pressure nanofiltration equipment includes membrane module,
High-pressure pump and production water pot.The composition of certain brine containing lithium: [Li+]=0.19g/L, [Mg2+]=23.75g/L, [Na+]=81.85g/
L, [K+]=7.52g/L.
1) tower heat reinforcing circulation spray concentration divides salt device salt reduction
High salinity brine, which is strengthened circulation spray concentration using tower heat, divides salt device to carry out circulation concentration, and brine volume is dense
9-10 times of contracting, potassium, sodium, magnesium salts are precipitated in the form of chloride solids in concentration process.
Strengthen circulation spray concentration through tower heat and divide salt device circular treatment, produces water after concentration: [Li+]=1.75g/L,
[Mg2+]=110.12g/L, [Na+]=8.19g/L, [K+]=2.27g/L.
2) high pressure nanofiltration demagging
By after concentration production water and intercrystalline water filter through micro-filtration, water after filter dilutes one times of feeding three-level high pressure nanofiltration,
Under 5Mpa pressure condition, concentrated brine is separated into nanofiltration concentrated water by nanofiltration membrane and nanofiltration produces water.Primary nanofiltration concentrated water is back to
Tower feed liquid mouth feed liquor, at remaining two-stage nanofiltration concentrate recirculation to upper level nanofiltration charging.Three-level produces water volume and receives compared to high pressure
Filter 3-4 times of feed brine volume concentration.
After circulation concentration, three-level high pressure nanofiltration processing, the high pressure nanofiltration third level produces the composition of water are as follows: [Li+]=
1.32g/L, [Mg2+]=11.23g/L, [Na+]=6.14g/L, [K+]=1.70g/L
3) high pressure nanofiltration produces water extraction and mentions lithium
Water lithium concentration is produced according to the high pressure nanofiltration third level, ferric trichloride is added with iron lithium molar ratio 2:1, by itself and organic extraction
System 60%TBP+40% sulfonated kerosene is taken to be extracted with 1: 1.5 volume ratio, extraction time 15min；It is with 6M hydrochloric acid
Stripping agent, the volume ratio for controlling organic phase and stripping agent is 10: 1, and rich lithium organic phase carries out level Four back extraction, single-stage back-extraction time
For 10min.The total recovery of lithium is 86.6%.
4) extractant, help extraction agent, raffinate and extractant regeneration cleaning solution reuse
Strip aqueous is evaporated+is dried under reduced pressure by water vapour, and regeneration hydrochloric acid and the compound chlorine of neutral monovalent metal containing lithium are obtained
Salt.After reverse-extraction of high acid mentions lithium, extractant must remove through low concentration alkali+neutral water cleaning and help extraction agent oily phase extract liquor, obtain again
Raw extractant.In extractant regeneration cleaning aqueous residue, removing is helped outside extraction agent, still containing the lithium of partial loss.It will be containing lithium
Extractant regeneration cleaning solution is mixed with raffinate raffinate, and water is added to adjust between pH=3-5, and extraction agent is helped to be hydrolyzed to iron hydroxide precipitation.
Residue removes the mixed liquor containing lithium for helping extraction agent, continues to be back to nanofiltration charging mouth, prevents lithium from losing, and improves the lithium rate of recovery.Hydrogen-oxygen
Change iron after the regeneration of hydrochloric acid that strip liquor steams, recycles iron chloride, energy-saving and emission-reduction.
5) liquid-solid extraction mentions lithium
Liquid-liquid extraction obtain it is neutral the monovalent metal containing lithium is compound chloride-based mentions lithium by ethyl alcohol liquid-solid extraction, recrystallize
High-purity lithium chloride products, extractant ethyl alcohol are recycled and are reused.
Embodiment 3
Mechanical thickening equipment is that tower heat reinforcing circulation spray concentration divides salt device, and high pressure nanofiltration equipment includes membrane module,
High-pressure pump and production water pot.The composition of certain brine containing lithium: [Li+]=0.83g/L, [Mg2+]=76.88g/L, [Na+]=23.50g/
L, [K+]=22.58g/L,
1) tower heat reinforcing circulation spray concentration divides salt device salt reduction
Lithium brine will be contained, strengthen circulation spray concentration using tower heat and salt device is divided to carry out circulation concentration, brine volume is dense
6-7 times of contracting, potassium, sodium, magnesium salts are precipitated in the form of chloride solids in concentration process.
Strengthen circulation spray concentration through tower heat and divide salt device circular treatment, produces water after concentration: [Li+]=4.98g/L,
[Mg2+]=109.05g/L, [Na+]=8.19g/L, [K+]=10.27g/L, [SO4 2-]=0.94g/L
2) high pressure nanofiltration demagging
By after concentration production water and intercrystalline water filter through micro-filtration, water after filter dilutes one times of feeding three-level high pressure nanofiltration,
Under 3Mpa pressure condition, concentrated brine is separated into nanofiltration concentrated water by nanofiltration membrane and nanofiltration produces water.Primary nanofiltration concentrated water is back to
Tower feed liquid mouth feed liquor, at remaining two-stage nanofiltration concentrate recirculation to upper level nanofiltration charging.Three-level produces water volume and receives compared to high pressure
Filter 3-4 times of feed brine volume concentration.
After circulation concentration, three-level high pressure nanofiltration processing, the high pressure nanofiltration third level produces the composition of water are as follows: [Li+]=
3.71g/L, [Mg2+]=12.81g/L, [Na+]=7.28g/L, [K+]=7.69g/L
3) high pressure nanofiltration produces water extraction and mentions lithium
Water lithium concentration is produced according to the high pressure nanofiltration third level, ferric trichloride is added with iron lithium molar ratio 2:1, by itself and organic extraction
System 60%TBP+40% sulfonated kerosene is taken to be extracted with 1: 1.5 volume ratio, extraction time 15min；It is with 6M hydrochloric acid
Stripping agent, the volume ratio for controlling organic phase and stripping agent is 10: 1, and rich lithium organic phase carries out level Four back extraction, single-stage back-extraction time
For 10min.The total recovery of lithium is 91.1%.
4) extractant, help extraction agent, raffinate and extractant regeneration cleaning solution reuse
Strip aqueous is evaporated+is dried under reduced pressure by water vapour, and regeneration hydrochloric acid and the compound chlorine of neutral monovalent metal containing lithium are obtained
Salt.After reverse-extraction of high acid mentions lithium, extractant must remove through low concentration alkali+neutral water cleaning and help extraction agent oily phase extract liquor, obtain again
Raw extractant.In extractant regeneration cleaning aqueous residue, removing is helped outside extraction agent, still containing the lithium of partial loss.It will be containing lithium
Extractant regeneration cleaning solution is mixed with raffinate raffinate, and water is added to adjust between pH=3-5, and extraction agent is helped to be hydrolyzed to iron hydroxide precipitation.
Residue removes the mixed liquor containing lithium for helping extraction agent, continues to be back to nanofiltration charging mouth, prevents lithium from losing, and improves the lithium rate of recovery.Hydrogen-oxygen
Change iron after the regeneration of hydrochloric acid that strip liquor steams, recycles iron chloride, energy-saving and emission-reduction.
5) liquid-solid extraction mentions lithium
The neutrality monovalent metal containing lithium that liquid-liquid extraction obtains is compound chloride-based to mention lithium by ethyl alcohol liquid-solid extraction, recrystallizes high
Purity lithium chloride products, extractant ethyl alcohol are recycled and are reused.
The basic principles, main features and advantages of the present invention have been shown and described above.Industry technology people
Member only illustrates the present invention described in above embodiments and specification it should be appreciated that the present invention is not limited to the above embodiments
Principle, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these variation and
Improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and equivalent
Object defines.
Claims (10)
1. a kind of tower heat, which strengthens circulation spray concentration, divides salt device, which is characterized in that including device noumenon, connect with device noumenon
Logical former brine case (1), described device ontology are circular tower type, and cavity internal upper part is equipped with spray equipment (2), and lower part is heat exchange type
Wind-guiding equipment (4), bottom are equipped with concentrated brine collecting pit (6)；Blower device is further connected in heat exchange type wind-guiding equipment (4)
(5)；It is set heat exchanger (8) in former brine case (1), heat exchanger (8), ground-source heat pump host (3), heat exchange type wind-guiding equipment (4) pass through
Pipeline forms the closed system filled with refrigerant；Brine is transported to spray equipment by former brine case (1) by brine pipeline and pump
(2), spray atomization is carried out.
2. the energy-saving and environment-friendly salt lake bittern that a kind of claim 1 described device uses proposes lithium technique, which is characterized in that including with
Lower step:
1) high salinity brine divides salt device circular treatment by tower heat reinforcing circulation spray concentration, makes in high salinity brine
Potassium, sodium, magnesium salts are precipitated with chloride and sulfuric acid salt loading mixed crystal, and obtain concentrated brine；Mixed crystal is through plate compression solid-liquid point
From respectively obtaining intercrystalline water containing lithium and mixed salt；
2) through tower heat strengthen circulation spray concentration divide salt device treated concentrated brine with it is miscellaneous through plate compression removing solid
The intercrystalline water containing lithium of matter dilutes to obtain nanofiltration raw water through water, and enters multistage pressure nanofiltration system；
3) multistep treatment Jing Guo high pressure nanofiltration divides salt to remove magnesium ion, respectively obtains level-one nanofiltration production water and the poor lithium of level-one is dense
Water；The poor lithium concentrated water of level-one is rich in magnesium ion concentrated water, is back at tower feed liquid mouth feed liquor, continues desalination, recycles rich lithium；
4) level-one nanofiltration produces water and obtains multistage pressure nanofiltration production water through multistage pressure nanofiltration technique, through neutral carrier+ferric trichloride
It helps and extracts lithium, respectively obtain the rich lithium organic phase of extraction and low lithium raffinate；Oil-water ratio is according to quality in extracting rich lithium organic phase
Than adding the back extraction of 6-8M hydrochloric acid for 10:1, rich lithium water phase and back extraction organic phase are respectively obtained；
5) rich lithium water phase is steamed sour technique and respectively obtains compound chloride-based containing lithium and regenerate hydrochloric acid；Organic phase is stripped through regeneration technology point
Regenerating extracting agent and extractant regeneration cleaning solution are not obtained, and regenerating extracting agent is back to use in the neutral carrier of step 4), and circulation makes
With；
6) extractant regeneration cleaning solution is mixed with the low lithium raffinate that step 4) obtains, and is added water to adjust pH > 3, is respectively obtained and help extraction
Agent hydroxide sediment and mixed liquor containing lithium；Mixed liquor containing lithium is back to the high pressure nanofiltration system of step 2), recycles lithium ion；
7) the regeneration mixed in hydrochloric acid for helping extraction agent hydroxide and step 5) to obtain of separation obtains regeneration and helps extraction agent, and regeneration helps extraction agent
It is back to use in the ferric trichloride of step 4)；
8) liquid-solid extraction is carried out with ethyl alcohol containing lithium is compound chloride-based by what is obtained after step 5) evaporation deacidification, respectively obtain compound chloride-based
With rich lithium organic phase, rich lithium organic phase obtains extraction organic phase and high-purity lithium chloride products through low-temperature evaporation.
3. a kind of energy-saving and environment-friendly salt lake bittern according to claim 2 proposes lithium technique, which is characterized in that in step 1),
Salt lake is tedded after producing salt, proposing the corresponding process of boron, lithium content between 0.15-2g/L, Mg/Li ratio counts in mass ratio 50~
Low lithium, Gao Mei, high salinity brine between 1000:1, after heat strengthens circulation by spraying, brine volume reaches 5-10 compared with raw water concentration
Times.
4. a kind of energy-saving and environment-friendly salt lake bittern according to claim 2 proposes lithium technique, which is characterized in that in step 2),
Nanofiltration raw water in the high pressure nanofiltration system, lithium content is between 1.5-10g/L, [Mg2+]=70-120g/L, Mg/Li ratio
Meter in mass ratio strengthens circulation spray concentration brine through heat and intercrystalline water mixing concentrated brine dilutes 1-2 between 10-100:1
Times, under 3-6MPa pressure, enter through nanofiltration membrane and produce water side, obtains nanofiltration and produce water and nanofiltration concentrated water.
5. a kind of energy-saving and environment-friendly salt lake bittern according to claim 4 proposes lithium technique, which is characterized in that in step 4),
The multistage pressure nanofiltration produces water and refers to [Li+]=1-8g/L, [Mg2+]=5-30g/L, Mg/Li ratio drop to 3-10:1, brine body
Product is compared with 3-5 times of concentration of nanofiltration water inlet.
6. a kind of energy-saving and environment-friendly salt lake bittern according to claim 2 proposes lithium technique, which is characterized in that in step 4),
It is that 1.5:1 adds neutral carrier according to grease mass ratio, is that 2:1 adds ferric trichloride with iron lithium molar ratio.
7. a kind of energy-saving and environment-friendly salt lake bittern according to claim 6 proposes lithium technique, which is characterized in that the neutral load
Body is the mixing organic phase that volume is 30-40% tributyl phosphate Yu 70-80% sulfonated kerosene.
8. a kind of energy-saving and environment-friendly salt lake bittern according to claim 2 proposes lithium technique, which is characterized in that in step 5),
The regeneration hydrochloric acid refers to, nanofiltration is produced water and is mentioned by extraction after the strip liquor after lithium evaporates+be dried under reduced pressure by water vapour
Recycle obtained rich lithium strip liquor middle and high concentration hydrochloric acid.
9. a kind of energy-saving and environment-friendly salt lake bittern according to claim 2 proposes lithium technique, which is characterized in that in step 5),
The extractant regeneration cleaning solution refers to: extraction organic phase through high concentrated acid back extraction mention lithium after, extractant must through low concentration alkali+in
Property water cleaning remove help extraction agent, obtain regenerating extracting agent and extractant regeneration cleaning solution；The low concentration alkali is the hydrogen-oxygen of 1-3M
Change sodium solution.
10. a kind of energy-saving and environment-friendly salt lake bittern according to claim 2 proposes lithium technique, which is characterized in that in step 6),
In extractant regeneration cleaning aqueous residue, removing is helped outside extraction agent, still contains some lithium, and the extractant regeneration containing lithium is cleaned
Liquid is mixed with raffinate raffinate, and water adjusting is added to make pH > 3, and extraction agent is helped to be hydrolyzed to iron hydroxide precipitation, and iron hydroxide and step 5) obtain
To regeneration mixed in hydrochloric acid obtain regeneration help extraction agent-iron chloride, the iron chloride of recycling can be back to use step 4)；Residue is removed and is helped
The mixed liquor containing lithium for extracting agent continues to be back to nanofiltration charging mouth, recycles low concentration lithium ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810135860.4A CN108359813B (en) | 2018-02-09 | 2018-02-09 | A kind of energy-saving and environment-friendly salt lake bittern proposes lithium technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810135860.4A CN108359813B (en) | 2018-02-09 | 2018-02-09 | A kind of energy-saving and environment-friendly salt lake bittern proposes lithium technique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108359813A CN108359813A (en) | 2018-08-03 |
| CN108359813B true CN108359813B (en) | 2019-10-01 |
Family
ID=63005539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810135860.4A Active CN108359813B (en) | 2018-02-09 | 2018-02-09 | A kind of energy-saving and environment-friendly salt lake bittern proposes lithium technique |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108359813B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220401885A1 (en) * | 2019-11-06 | 2022-12-22 | Fluid Technology Solutions (fts) Inc. | Methods and systems for reducing magnesium in high salinity salar brines by nanofiltration and forward osmosis |
| CN111793755A (en) * | 2020-08-03 | 2020-10-20 | 苏州增华新能源科技有限公司 | Organic phase online purification method and device in lithium extraction process of salt lake and application |
| CN112850851B (en) * | 2021-02-01 | 2022-04-15 | 中国科学院青海盐湖研究所 | Method for increasing Li content in sodium sulfate subtype salt lake brine+Method of yield |
| CN115558798B (en) * | 2021-07-02 | 2023-12-01 | 浙江新化化工股份有限公司 | Method for producing lithium compound |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408705C (en) * | 2003-04-30 | 2008-08-06 | 中国科学院青海盐湖研究所 | Nano-filtration method for separating magnesium and enriching lithium from salt lake brine |
| CN101385904A (en) * | 2008-10-06 | 2009-03-18 | 陆立勇 | Brine concentration method |
| CN102976540B (en) * | 2012-09-24 | 2014-12-03 | 赵贵 | Tower type solar energy-wind energy seawater vaporization water production apparatus |
| CN103074502B (en) * | 2013-01-29 | 2014-04-23 | 中国科学院青海盐湖研究所 | Salt lake brine treatment method for separating lithium from high-magnesium-lithium-ratio salt lake brine |
| CN103405941B (en) * | 2013-07-25 | 2015-05-20 | 杭州求是透平机制造有限公司 | Cooling tower type evaporation system |
| RU2582031C1 (en) * | 2015-06-09 | 2016-04-20 | Александр Алексеевич Соловьев | Aerodynamic cooling tower with external heat exchange |
| CN105152190B (en) * | 2015-09-18 | 2017-04-05 | 湘潭大学 | A kind of method that separating magnesium from low lithium salt and enriching lithium produce lithium carbonate |
| CN106636673B (en) * | 2016-12-23 | 2018-08-31 | 江西合纵锂业科技有限公司 | A method of lithium is extracted from salt lake bittern using extraction |
-
2018
- 2018-02-09 CN CN201810135860.4A patent/CN108359813B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108359813A (en) | 2018-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108359813B (en) | A kind of energy-saving and environment-friendly salt lake bittern proposes lithium technique | |
| CN108341420B (en) | Method for directly preparing lithium hydroxide and lithium carbonate from salt lake brine with high magnesium-lithium ratio | |
| CN103553138B (en) | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water | |
| CN109650414A (en) | High impurity lithium source prepares LITHIUM BATTERY, the method and system of high-purity grade of lithium hydroxide and lithium carbonate | |
| CN105540619B (en) | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio | |
| CN107298450A (en) | The method that lithium hydroxide and lithium carbonate are prepared using soluble lithium salt solution | |
| CN109650415B (en) | Method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder | |
| CN107366005B (en) | A kind of process of sodium sulphate type bittern perhalogeno ionic membrane caustic soda by-product anhydrous sodium sulphate | |
| CN109319998A (en) | A kind of the near-zero release processing system and technique of ternary precursor material production waste water | |
| CN109803924A (en) | The preparation method of lithium compound | |
| CN110422863A (en) | A method of preparing battery-stage monohydrate lithium hydroxide | |
| CN109252168A (en) | A kind of devices and methods therefor of efficient activated acid etching solution | |
| CN108439438A (en) | The method that nickel cobalt mn sulphate and lithium carbonate are prepared by waste and old ternary battery material | |
| CN204417276U (en) | A kind of Coal Chemical Industry strong brine evaporative crystallization divides salt device | |
| CN106399715A (en) | Method for producing electrolytic zinc through high-chloride zinc ash material ammonia leaching ion exchange combined process | |
| CN208893656U (en) | The equipment of NMP recycling heat pump distillation in a kind of production of lithium electricity | |
| CN103193238B (en) | Method for producing superfine white carbon black, ferric hydroxide and aluminum oxide by using coal ash | |
| CN103725888A (en) | Method for extracting nickel from copper electrolysis effluent | |
| CN103408046B (en) | Method for separating sodium and magnesium from laterite-nickel ore smelting primary wastewater | |
| CN105130079A (en) | Treatment process combining H acid mother solution and T acid mother solution | |
| CN102628105B (en) | Method for comprehensively recycling and using baric waste slag in refined aluminum production process | |
| CN108341421B (en) | Method for directly preparing lithium carbonate from salt lake brine with high magnesium-lithium ratio | |
| CN108314066A (en) | A kind of poor lithium brine salt reduction richness lithium method and its device | |
| CN105540975B (en) | A kind of recycling processing method and its system of PCB circuit board etching waste liquor | |
| CN104577122B (en) | Lithium iron phosphate solvothermal preparation device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200220 Address after: Room 301, Membrane Separation Technology Research Institute, No. 13, middle section of Yanta Road, Beilin District, Xi'an City, Shaanxi Province Patentee after: Xi'an jinzang membrane Environmental Protection Technology Co., Ltd Address before: 710075 S205 building, 25 new hi tech Road, hi tech Zone, Xi'an, Shaanxi Patentee before: Shaanxi Membrane Separation Technology Research Institute Co Ltd |