CN107828960B - The collaboration extraction system and its processing method of magnesium and lithium in a kind of salt lake bittern - Google Patents

The collaboration extraction system and its processing method of magnesium and lithium in a kind of salt lake bittern Download PDF

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CN107828960B
CN107828960B CN201711091350.3A CN201711091350A CN107828960B CN 107828960 B CN107828960 B CN 107828960B CN 201711091350 A CN201711091350 A CN 201711091350A CN 107828960 B CN107828960 B CN 107828960B
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magnesium
liquid
temperature
tower
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CN107828960A (en
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杨刚
谢旭阳
王云山
杨朝勇
安学斌
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Beijing Jixiang Sightsee Technology Development Co ltd
Institute of Process Engineering of CAS
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Beijing Jixiang Sightsee Technology Development Co ltd
Institute of Process Engineering of CAS
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    • 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
    • C22B3/02—Apparatus therefor
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

The present invention provides the collaboration extraction system and its processing method of magnesium in a kind of salt lake bittern and lithium, the collaboration extraction system mainly includes spray roasting system, dust pelletizing system, slurrying wash mill, equipment for separating liquid from solid, mentions magnesium unit, mentions lithium unit and smoke processing system；Wherein, the product for mentioning magnesium unit includes magnesia, and the product for mentioning lithium unit includes magnesium hydrate precipitate and lithium carbonate, mentions magnesium unit described in the magnesium hydrate precipitate entrance and carries out mentioning magnesium.Wet process Reaction Separation and pyrogenic process are purified organic coupling by the present invention, the conventional process techniques of salt lake bittern element extraction are integrated, realize that the high-valued collaboration of valuable element magnesium and lithium in salt lake bittern is extracted, fume afterheat is made full use of in extraction process simultaneously, realize heat cascade utilization, no waste water and waste residue generate, and tail gas qualified discharge belongs to a kind of greenization cleaner technology.

Description

The collaboration extraction system and its processing method of magnesium and lithium in a kind of salt lake bittern
Technical field
The invention belongs to salt lake bittern Resource Access field, it is related to the collaboration extraction system of magnesium and lithium in a kind of salt lake bittern And its processing method.
Background technique
With petering out for global fossil energy, lithium has become the ideal material of the 21 century energy and light alloy, The important element for referred to as world being pushed to advance has important in fields such as high-energy battery, aerospace and nuclear fusion power generations Purposes.Magnesium is similar with lithium, and the various uses with light metal, magnesia is a kind of its most important oxide, has excellent The performances such as alkaline-resisting, heat-resisting and insulation, it is widely used.
Salt lake bittern is resourceful, is rich in a variety of valuable elements, and salt lake bittern passes through salt manufacturing, extracts boron, potassium, bromine, iodine etc. After element, there are about 80% or so lithiums and most magnesium to stay in mother liquor.Compared with mentioning lithium from ore, salt lake mentions lithium more It is easy, cost is lower, therefore, brine, which mentions lithium ore is replaced to mention lithium, has become development trend.
The element as contained by salt lake bittern is numerous, and especially magnesium is similar with two kinds of element physicochemical properties of lithium, and separating difficulty is big. Currently, having from the main method of extracting lithium from salt lake brine: (1) precipitation method, (2) aluminate method, (3) ion exchange adsorption, (4) Carbonizatin method and (5) solvent extraction.1618997 A of patent CN provides the side of a kind of combined extracting magnesium, lithium from salt lake bittern Method is realized that magnesium, lithium efficiently separating and extracting, is produced a set of magnesium products and lithium carbonate using two sections of magnesium sinkings of ammonia and ammonium hydrogen carbonate, The circulation that this method is related to ammonia is similar with other precipitation method, and reliability of technology is preferable, but process flow is more complex；Patent CN 106430254 A disclose a kind of method from extracting lithium from salt lake brine, which produces aluminium salt with activation kaolin salt Ore Leaching, It is then added to salt lake bittern to be reacted, obtains precipitating containing lithium, it is similar with other aluminate methods, although alkaline consumption is low, water Evaporation is big, and processing cost is higher；104925836 A of patent CN provides a kind of ion-exchange absorption that lithium is mentioned from brine containing lithium Attached method, this method is selectively good, and the rate of recovery is high, but adsorbing the problems such as resin is at high cost, the service life is short and regeneration is difficult becomes master Want restraining factors；1335263 A of patent CN provides a kind of method for being carbonized and mentioning lithium, and this method adds first in salt lake bittern Enter precipitating reagent, so that Mg2+And Li+It is precipitated out, then lithium precipitating dissolution is made by carbonization or carbonation, reach magnesium lithium point From effect, lithium carbonate is finally made, carbonizatin method is at low cost, it is easy to accomplish industrialization, but yield is low, furthermore there is titanium dioxide Carbon carrys out source problem；102001692 A of patent CN provides the synergistic system that a kind of salt lake bittern extraction mentions lithium, institute It is selectively preferable with extraction, but there are problems that equipment seriously corroded and extractant loss, higher cost.
In conclusion existing method is multiple to mention lithium single, resource utilization is not high, less economical, and exists certain Therefore problem if how easier method, lower cost realize that the collaboration of magnesium and lithium is extracted, realizes that Brine resources are efficient Using be salt lake bittern exploitation urgent problem.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides the collaborations of magnesium and lithium in a kind of salt lake bittern to extract system System and its processing method.The present invention utilizes hydrometallurgy and the respective advantage of pyrometallurgy, and wet process Reaction Separation and pyrogenic process are mentioned Pure organic coupling integrates the conventional process techniques of salt lake bittern element extraction, realizes element magnesium and lithium in salt lake bittern High-valued collaboration extract；It makes full use of fume afterheat simultaneously, realizes heat cascade utilization, without waste water and waste residue in extraction process It generates, tail gas qualified discharge belongs to a kind of greenization cleaner technology.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention provides the collaboration extraction system of magnesium in a kind of salt lake bittern and lithium, system is extracted in the collaboration System mainly include spray roasting system, dust pelletizing system, slurrying wash mill, equipment for separating liquid from solid, mention magnesium unit, mention lithium unit and Smoke processing system；Wherein, the material outlet of the spray roasting system is connected with the material inlet of the dust pelletizing system, described The exhanst gas outlet of dust pelletizing system is connected with the gas access of the smoke processing system, the solid matter outlet of the dust pelletizing system Successively be connected with the slurrying wash mill and equipment for separating liquid from solid, the solid matter outlet of the equipment for separating liquid from solid with it is described The material inlet for mentioning magnesium unit is connected, the liquid outlet of the equipment for separating liquid from solid and the material inlet phase for mentioning lithium unit Even, the product for mentioning magnesium unit includes magnesia, and the product for mentioning lithium unit includes magnesium hydrate precipitate and lithium carbonate, institute State magnesium hydrate precipitate enter described in mention magnesium unit and carry out mentioning magnesium.
In the present invention, the collaboration extraction system comprehensive utilization wet process and pyrogenic process purification technique pass through the phase between each system It connects, effective reuse of material greatly improves the yield that magnesium and lithium collaboration are extracted in salt lake bittern, realizes that its is high-valued It utilizes.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the spray roasting system includes air compressor machine and spray roasting tower, described The gas vent of air compressor machine is connected with the bottom gas inlet of spray roasting tower.
Preferably, the dust pelletizing system includes cyclone separator and bag filter, and the flue gas of the cyclone separator goes out Mouth is connected with the entrance of bag filter.
In the present invention, the spray roasting tower outlet material is introduced into cyclone separator, enters back into bag filter, in this way Be provided in just leave spray roasting tower temperature of charge it is higher, general bag filter is difficult to meet the temperature requirement；Institute The solid matter outlet for stating cyclone separator and bag filter is connected with the slurrying wash mill, and flue gas by removing twice Dirt, so that gas is sufficiently separated with solid, to improve the yield of product.
Preferably, the magnesium unit that mentions includes sequentially connected first slurrying wash mill, the first equipment for separating liquid from solid, The liquid outlet of two slurrying wash mills, the second equipment for separating liquid from solid and calcining furnace, first equipment for separating liquid from solid obtains chlorine Change sodium solution, the liquid outlet of second equipment for separating liquid from solid is connected with the top entry of the first slurrying wash mill, described The solid outlet of second equipment for separating liquid from solid is connected with the entrance of calcining furnace.
Preferably, the lithium unit that mentions includes sequentially connected evaporator, the first settler, third separation of solid and liquid dress It sets, the second settler and the 4th equipment for separating liquid from solid, the evaporator condensation liquid export the top with the second slurrying wash mill Portion's entrance is connected, and the solid outlet of the third equipment for separating liquid from solid is connected with the top entry of the first slurrying wash mill, institute It is also connected with conveyer after stating the 4th equipment for separating liquid from solid, it is molten that the liquid outlet of the 4th equipment for separating liquid from solid obtains sodium chloride Liquid.
In the present invention, the magnesium hydrate precipitate that first settler generates mentions magnesium back to described after being separated by solid-liquid separation First slurrying wash mill of unit, can effectively improve the recovery rate of magnesium elements in salt lake bittern, avoids the waste of resource, Better economy.
Preferably, before the bottom inlet of the spray roasting tower, between slurrying wash mill and equipment for separating liquid from solid, first Between slurrying wash mill and the first equipment for separating liquid from solid, the second slurrying wash mill and second be separated by solid-liquid separation dress between, first Pump is equipped between the second settler and the 4th equipment for separating liquid from solid between settler and third equipment for separating liquid from solid.
As currently preferred technical solution, the air compressor machine is screw compressor or piston compressor.
Preferably, the cyclone separator includes single tube cyclone dust collectors and/or multi-tube dust cleaner.
Preferably, the equipment for separating liquid from solid, the first equipment for separating liquid from solid, the second equipment for separating liquid from solid, third solid-liquid point It is filter device or centrifugal device, preferably plate and frame filter press from device and the 4th equipment for separating liquid from solid.
Preferably, the evaporator is triple effect falling film evaporator.
Preferably, the pump is the group of any one in centrifugal pump, reciprocating pump, rotary pump or peripheral pump or at least two It closes, the combination is typical but non-limiting example has: the combination of the combination of centrifugal pump and reciprocating pump, centrifugal pump and rotary pump, it is past The combination of multiple pump and peripheral pump, the combination of reciprocating pump, rotary pump and peripheral pump, centrifugal pump, reciprocating pump and combination of peripheral pump etc..
As currently preferred technical solution, the smoke processing system includes neutralizing absorption tower and mist projection granulating tower, The outlet at bottom for neutralizing absorption tower is connected with the liquid inlet of mist projection granulating tower, and the outlet of the mist projection granulating tower obtains chlorine Change calcium product.
Preferably, the smoke processing system further includes heat exchanger and calcification sizing device, the heat of the heat exchanger Fluid inlet is connected with the exhanst gas outlet of the bag filter, and the hot fluid outlet ports of the heat exchanger and the neutralization absorb The bottom gas inlet of tower is connected, and the outlet of the calcification sizing device is connected with the bottom slurry import for neutralizing absorption tower.
Preferably, circulating pump, the entrance of the circulating pump and institute are equipped between neutralization absorption tower and the mist projection granulating tower The outlet at bottom for stating neutralization absorption tower is connected, the outlet of the circulating pump and the top entry and mist projection granulating tower that neutralize absorption tower Liquid inlet be connected.
As currently preferred technical solution, the heat exchanger is tubular heat exchanger.
Preferably, the neutralization absorption tower is three-level circulating absorption tower.
Preferably, the circulating pump is any one in centrifugal pump, reciprocating pump, rotary pump or peripheral pump.
Second aspect, the present invention provides the processing methods of above-mentioned collaboration extraction system, the described method comprises the following steps:
(a) salt lake bittern is subjected to spray roasting, then obtains solid material and flue gas through dust removal process；
(b) solid material that step (a) obtains is subjected to slurrying washing and obtained after being separated by solid-liquid separation liquid material containing lithium with Solid material containing magnesium；
(c) solid material containing magnesium that step (b) obtains is obtained into magnesium hydroxide through multipolarity plasm scouring and after being separated by solid-liquid separation Solid, then magnesia is obtained through calcining；
(d) liquid material containing lithium for obtaining step (b) is successively concentrated by evaporation, after multi stage precipitation reaction and separation of solid and liquid Magnesium hydroxide and lithium carbonate are obtained, obtained magnesium hydroxide return step (c) is handled.
As currently preferred technical solution, step (a) salt lake bittern refers to after extracting potassium, sodium and bromine Based on magnesium chloride, the solution containing lithium chloride and sodium chloride, wherein content of magnesium be 80-150g/L, such as 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, 140g/L or 150g/L etc., it is not limited to cited numerical value, the numerical value Other unlisted numerical value are equally applicable in range；Chlorinity is 260-500g/L, for example, 260g/L, 290g/L, 320g/L, 350g/L, 380g/L, 410g/L, 440g/L, 470g/L or 500g/L etc., it is not limited to cited numerical value, the numerical value Other unlisted numerical value are equally applicable in range；Lithium content is 4-8g/L, such as 4g/L, 4.5g/L, 5g/L, 5.5g/L, 6g/ L, 6.5g/L, 7g/L, 7.5g/L or 8g/L etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value it is equally applicable；Sodium content is 1-2g/L, such as 1g/L, 1.2g/L, 1.4g/L, 1.6g/L, 1.8g/L or 2g/L etc., It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (a) the salt lake bittern feeding temperature be 30-50 DEG C, such as 30 DEG C, 33 DEG C, 36 DEG C, 39 DEG C, 42 DEG C, 45 DEG C, 48 DEG C or 50 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range It is equally applicable.
Preferably, step (a) spray roasting needs to be passed through compressed air, and the compressed air is provided by air compressor machine.
Preferably, the compressed air pressure be 0.4-0.6MPa, such as 0.4MPa, 0.42MPa, 0.45MPa, 0.48MPa, 0.5MPa, 0.53MPa, 0.55MPa, 0.57MPa or 0.6MPa etc., it is not limited to cited numerical value, it should Other unlisted numerical value are equally applicable in numberical range；Intake air temperature be 30-50 DEG C, such as 30 DEG C, 33 DEG C, 36 DEG C, 39 DEG C, 42 DEG C, 45 DEG C, 48 DEG C or 50 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range It is equally applicable.
Preferably, the compressed air and salt lake bittern volume ratio are (90-120): 1, such as 90:1,95:1,100:1, 105:1,110:1,115:1 or 120:1 etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value is equally applicable.
Preferably, step (a) spray roasting is carried out in the case where fuel provides heat condition.
Preferably, the fuel is any one in methanol, diesel oil, liquefied gas or natural gas.
In the present invention, fuel used general single use, it is possible to prevente effectively from fuel is used in mixed way the explosion be easy to causeing It is dangerous.
Preferably, step (a) spray roasting carries out in spray roasting tower.
Preferably, the spray roasting column bottom temperature be 600-800 DEG C, such as 600 DEG C, 630 DEG C, 660 DEG C, 690 DEG C, 720 DEG C, 750 DEG C, 780 DEG C or 800 DEG C etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value is equally applicable；Head temperature is 350-550 DEG C, such as 350 DEG C, 380 DEG C, 400 DEG C, 430 DEG C, 450 DEG C, 480 DEG C, 500 DEG C, 520 DEG C or 550 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value are equally suitable in the numberical range With.
Preferably, in the spray roasting tower residence time of material be 2-6s, such as 2s, 2.5s, 3s, 3.5s, 4s, 4.5s, 5s, 5.5s or 6s etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same It is applicable in, preferably 3-5s.
Preferably, the spray roasting tower outlet mass temperatures be 300-500 DEG C, such as 300 DEG C, 330 DEG C, 360 DEG C, 390 DEG C, 420 DEG C, 450 DEG C, 480 DEG C or 500 DEG C etc., it is not limited to cited numerical value, in the numberical range, other are not The numerical value enumerated is equally applicable.
Preferably, step (a) dust removal process carries out in cyclone separator and bag filter respectively.
Preferably, the bag filter input gas temperature be 220-320 DEG C, such as 220 DEG C, 240 DEG C, 260 DEG C, 280 DEG C, 300 DEG C or 320 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same Sample is applicable in, and preferably 250-300 DEG C.
Preferably, the bag filter exit gas temperature be 200-300 DEG C, such as 200 DEG C, 220 DEG C, 240 DEG C, 260 DEG C, 280 DEG C or 300 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same Sample is applicable in, and preferably 220-280 DEG C.
In the present invention, the flue-gas temperature into bag filter cannot be too high, and otherwise bag filter is difficult to bear, therefore Need to first pass through cyclone separator separation and cooling；The flue-gas temperature for leaving bag filter should not be too low, and temperature is too low, cigarette Acid gas in gas easily becomes acid solution, and bag filter is caused to block.
Preferably, step (b) and step (c) washing are countercurrent washing.
Preferably, step (b) and described be separated by solid-liquid separation of step (c) are to be separated by filtration.
Preferably, step (b) and the washing of step (c) slurrying and to be separated by solid-liquid separation operation temperature be 50-90 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C etc., it is not limited to cited numerical value, the numerical value Other unlisted numerical value are equally applicable in range, and preferably 60-80 DEG C.
Preferably, step (c) the multipolarity plasm scouring and separation of solid and liquid are that two-stage slurrying is washed and is separated by solid-liquid separation.
Preferably, step (c) calcining carries out in calcining furnace.
Preferably, step (c) calcination temperature is 400-800 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 800 DEG C etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value it is equally applicable, preferably 550-750 DEG C, further preferably 600-700 DEG C.
Preferably, step (c) calcination time is 0.5-2h, such as 0.5h, 0.75h, 1h, 1.25h, 1.5h, 1.75h Or 2h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 0.8-1.2h。
Preferably, in step (c) magnesium oxide product content of magnesia be greater than 98wt%, such as 98.1wt%, 98.4wt%, 98.7wt%, 99.0wt%, 99.3wt%, 99.6wt% or 99.9wt% etc., it is not limited to cited Numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (d) evaporation and concentration carries out in evaporator.
Preferably, step (d) evaporation and concentration is using steam as heat source.
Preferably, 120-160 DEG C of the inlet steam temperature, for example, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C or 160 DEG C etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value is equally applicable, and preferably 130-150 DEG C.
Preferably, the steam condensate outlet temperature be 60-90 DEG C, such as 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, excellent It is selected as 70-80 DEG C.
Preferably, step (d) the multi stage precipitation reaction and separation of solid and liquid are respectively level-one precipitation reaction and separation of solid and liquid And two-stage precipitation is reacted and is separated by solid-liquid separation.
Preferably, the level-one precipitation reaction is magnesium sinking reaction, using sodium hydroxide as precipitating reagent.
Preferably, the level-one precipitation reaction temperature is 50-90 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value are same in the numberical range Sample is applicable in, and preferably 60-80 DEG C.
Preferably, the level-one precipitation reaction time be 10-40min, such as 10min, 15min, 20min, 25min, 30min, 35min or 40min etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same Sample is applicable in.
Preferably, the two-stage precipitation reaction is that sinker reacts, using sodium carbonate as precipitating reagent.
Preferably, the two-stage precipitation reaction temperature is 50-90 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value are same in the numberical range Sample is applicable in, and preferably 60-80 DEG C.
Preferably, the precipitation reaction time described in the second level be 20-50min, such as 20min, 25min, 30min, 35min, 40min, 45min or 50min etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value is equally applicable.
Preferably, step (d) is described is separated by solid-liquid separation to be separated by filtration, and operation temperature is 50-90 DEG C, for example, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C etc., it is not limited to cited numerical value, in the numberical range its His unlisted numerical value is equally applicable, and preferably 60-80 DEG C.
As currently preferred technical solution, the flue gas that step (a) is obtained is handled, processing method include with Lower step:
(A) flue gas for obtaining step (a) carries out neutralization absorption after heat exchange, obtains calcium chloride solution, and tail gas is up to standard Discharge；
(B) calcium chloride solution that step (A) obtains is obtained into calcium chloride product through mist projection granulating.
As currently preferred technical solution, step (A) described heat exchange is using air as cold source.
Preferably, after step (A) described heat exchange air themperature be 150-230 DEG C, such as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C or 230 DEG C etc., it is not limited to cited numerical value, in the numberical range Other unlisted numerical value are equally applicable, and preferably 170-210 DEG C.
Preferably, after step (A) described heat exchange flue-gas temperature be 120-180 DEG C, such as 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C or 180 DEG C etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value is equally applicable, and preferably 130-150 DEG C.
Preferably, step (A) neutralization is absorbed in and is carried out in absorption tower.
Preferably, step (A) neutralization is absorbed using milk of lime as neutralizer, mass concentration 5%-10%, such as 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10% etc., it is not limited to cited Numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the milk of lime is handled to obtain by lime and water through slurrying.
Preferably, the slurrying processing carries out in calcification sizing device.
Preferably, step (A) the hydrogen chloride in tail gas content be not more than 10ppm, such as 10ppm, 9ppm, 8ppm, 7ppm, 6ppm, 5ppm, 4ppm, 3ppm, 2ppm or 1ppm etc., it is not limited to cited numerical value, in the numberical range its His unlisted numerical value is equally applicable, preferably not greater than 5ppm.
Preferably, step (B) described mist projection granulating carries out in mist projection granulating tower.
Preferably, step (B) mist projection granulating is using the air after step (A) heat exchange as heat source.
As currently preferred technical solution, the described method comprises the following steps:
(I) the temperature salt lake bittern for being 30-50 DEG C and pressure is 0.4-0.6Mpa, temperature is 30-50 DEG C compression is empty Gas enters spray roasting tower in the case where fuel provides heat condition and is roasted, and wherein compressed air is with salt lake bittern volume ratio (90-120): 1, spray roasting column bottom temperature is 600-800 DEG C, and head temperature is 350-550 DEG C, when material stops in tower Between be 3-5s, spray roasting top of tower outlet mass temperatures be 300-500 DEG C, sequentially enter cyclone separator and bag filter It is dusted processing, obtains solid material and flue gas, flue-gas temperature is 250-300 DEG C when into bag filter, leaves cloth bag Flue-gas temperature is 220-280 DEG C when deduster；
(II) solid material that step (I) obtains is subjected to slurrying, countercurrent washing and is separated by filtration processing, operation temperature is 60-80 DEG C, obtain liquid material containing lithium and solid material containing magnesium；
(III) flue gas for obtaining step (I) carries out heat exchange with air in a heat exchanger, leaves heat exchanger space-time Temperature degree be 170-210 DEG C, flue-gas temperature be 130-150 DEG C, the flue gas after leaving enter neutralize absorption tower, with come from calcification The milk of lime contact that the mass concentration of sizing device is 5%-10% carries out neutralization absorption, and emptying hydrogen chloride in tail gas concentration is not higher than 5ppm, acquired solution enter mist projection granulating tower, make heat source progress mist projection granulating to leave the air of heat exchanger, obtain calcium chloride Product；
(IV) solid material containing magnesium that step (II) obtains through two-stage slurrying, countercurrent washing and is separated by filtration processing again, Operation temperature is 60-80 DEG C, obtains magnesium hydroxide solid, gained magnesium hydroxide solid is calcined under the conditions of 600-700 DEG C 0.8-1.2h obtains the high-purity magnesium oxide that content of magnesia is greater than 98%；
(V) liquid material containing lithium that step (II) obtains is evaporated concentration in evaporator, with 130-150 DEG C Steam is heat source, and the solution after concentration carries out magnesium sinking reaction by precipitating reagent of sodium hydroxide, and reaction temperature is 60-80 DEG C, reaction Time is 10-40min, is separated by filtration under the conditions of 60-80 DEG C, and obtained magnesium hydroxide return step (IV) is handled, and is obtained The solution arrived carries out sinker reaction by precipitating reagent of sodium carbonate again, and reaction temperature is 60-80 DEG C, reaction time 20-50min, It is separated by filtration under the conditions of 60-80 DEG C, obtains lithium carbonate product and sodium chloride solution.
Compared with prior art, the invention has the following advantages:
(1) system of the present invention is combined with each other, and the technical process is mutually integrated, by Reaction Separation and purifies organic coupling It closes, is extracted by the multi-level collaborative of magnesium in salt lake bittern and lithium and realize that in high yield, the yield of lithium reaches 93% or more, the yield of magnesium Up to 98% or more；
(2) System and method for of the present invention industrializing implementation, products obtained therefrom seriation, high-valued, energy is reasonable Cascade utilization, Atom economy are significant；
(3) present invention is generated without waste water and waste residue, exhaust gas qualified discharge, and process cleans environmental protection is valuable in salt lake bittern The synthesis of element provides new approach.
Detailed description of the invention
Fig. 1 is the device connection schematic diagram that extraction system is cooperateed with described in the embodiment of the present invention 1；
Fig. 2 is the process flow diagram that extraction system is cooperateed with described in the embodiment of the present invention 3；
Wherein, 1- air compressor machine, 2- spray roasting tower, 3- cyclone separator, 4- bag filter, 5- heat exchanger, 6- stone It is ashed sizing device, in 7- and absorption tower, 8- mist projection granulating tower, 9- slurrying wash mill, 10- equipment for separating liquid from solid, 11- first changes Plasm scouring device, the first equipment for separating liquid from solid of 12-, 13- the second slurrying wash mill, the second equipment for separating liquid from solid of 14-, 15- are forged Burning furnace, 16- evaporator, the first settler of 17-, 18- third equipment for separating liquid from solid, the second settler of 19-, 20- the 4th are solid Liquid separating apparatus, 21- conveyer.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this Invention protection scope is subject to claims.
Specific embodiment of the invention part provides the collaboration extraction system and its place of magnesium and lithium in a kind of salt lake bittern Reason method, the collaboration extraction system mainly include spray roasting system, dust pelletizing system, slurrying wash mill 9, are separated by solid-liquid separation dress 10 are set, magnesium unit is mentioned, mentions lithium unit and smoke processing system；Wherein, the material outlet of the spray roasting system is removed with described The material inlet of dirt system is connected, and the exhanst gas outlet of the dust pelletizing system is connected with the gas access of the smoke processing system, The solid matter outlet of the dust pelletizing system is successively connected with the slurrying wash mill 9 and equipment for separating liquid from solid 10, described solid The solid matter outlet of liquid separating apparatus 10 is connected with the material inlet for mentioning magnesium unit, the liquid of the equipment for separating liquid from solid 10 Body outlet is connected with the material inlet for mentioning lithium unit, and the product for mentioning magnesium unit includes magnesia, described to mention lithium unit Product include magnesium hydrate precipitate and lithium carbonate, the magnesium hydrate precipitate enter described in mention magnesium unit and carry out mentioning magnesium.
Its processing method the following steps are included:
(a) salt lake bittern is subjected to spray roasting, then obtains solid material and flue gas through dust removal process；
(b) solid material that step (a) obtains is subjected to slurrying washing and obtained after being separated by solid-liquid separation liquid material containing lithium with Solid material containing magnesium；
(c) solid material containing magnesium that step (b) obtains is obtained into magnesium hydroxide through multipolarity plasm scouring and after being separated by solid-liquid separation Solid, then magnesia is obtained through calcining；
(d) liquid material containing lithium for obtaining step (b) is successively concentrated by evaporation, after multi stage precipitation reaction and separation of solid and liquid Magnesium hydroxide and lithium carbonate are obtained, obtained magnesium hydroxide return step (c) is handled.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
The collaboration extraction system of magnesium and lithium in a kind of salt lake bittern is present embodiments provided, as shown in Figure 1, the collaboration mentions To take system mainly include spray roasting system, dust pelletizing system, slurrying wash mill 9, plate and frame filter press 10, mentions magnesium unit, mentions lithium Unit and smoke processing system；Wherein, the material inlet phase of the material outlet of the spray roasting system and the dust pelletizing system Even, the exhanst gas outlet of the dust pelletizing system is connected with the gas access of the smoke processing system, the solid of the dust pelletizing system Material outlet is successively connected with the slurrying wash mill 9 and plate and frame filter press 10, the solid material of the plate and frame filter press 10 Outlet is connected with the material inlet for mentioning magnesium unit, the liquid outlet of the plate and frame filter press 10 and the object for mentioning lithium unit Expect entrance be connected, the product for mentioning magnesium unit includes magnesia, the product for mentioning lithium unit include magnesium hydrate precipitate and Lithium carbonate, the magnesium hydrate precipitate enter described in mention magnesium unit and carry out mentioning magnesium.
The spray roasting system includes screw compressor 1 and spray roasting tower 2, the gas of the screw compressor 1 Body outlet is connected with the bottom gas inlet of spray roasting tower 2.
The dust pelletizing system includes single tube cyclone dust collectors 3 and bag filter 4, the cigarette of the single tube cyclone dust collectors 3 Gas outlet is connected with the entrance of bag filter 4.
The magnesium unit that mentions includes sequentially connected first slurrying wash mill 11, the change of the first plate and frame filter press 12, second Plasm scouring device 13, the second plate and frame filter press 14 and calcining furnace 15, the liquid outlet of first plate and frame filter press 12 obtain chlorine Change sodium solution, the liquid outlet of second plate and frame filter press 14 is connected with the top entry of the first slurrying wash mill 11, institute The solid outlet for stating the second plate and frame filter press 14 is connected with the entrance of calcining furnace 15.
The lithium unit that mentions includes sequentially connected triple effect falling film evaporator 16, the first settler 17, third sheet frame pressure Filter 18, the second settler 19 and the 4th plate and frame filter press 20,16 condensate outlet of triple effect falling film evaporator and second The top entry of slurrying wash mill 13 is connected, the solid outlet of the third plate and frame filter press 18 and the first slurrying wash mill 11 top entry is connected, and conveyer 21, the 4th plate and frame filter press 20 are also connected with after the 4th plate and frame filter press 20 Liquid outlet obtain sodium chloride solution.
Before the bottom inlet of the spray roasting tower 2, between slurrying wash mill 9 and plate and frame filter press 10, the first slurrying Between wash mill 11 and the first plate and frame filter press 12, between the second slurrying wash mill 13 and the second plate and frame filter press 14, It is all provided between the second settler 19 and the 4th plate and frame filter press 20 between one settler 17 and third plate and frame filter press 18 There is centrifugal pump.
The smoke processing system includes tubular heat exchanger 5, calcification sizing device 6, three-level circulating absorption tower 7 and is sprayed Granulation tower 8, the thermal fluid inlet of the tubular heat exchanger 5 are connected with the exhanst gas outlet of the bag filter 4, the tubulation The hot fluid outlet ports of formula heat exchanger 5 are connected with the bottom gas inlet of the three-level circulating absorption tower 7, the calcification sizing device 6 outlet is connected with the bottom slurry import of three-level circulating absorption tower 7, the three-level circulating absorption tower 7 and mist projection granulating tower 8 it Between be equipped with centrifugal pump, the entrance of the centrifugal pump is connected with the outlet at bottom of the three-level circulating absorption tower 7, the centrifugal pump Outlet is connected with the liquid inlet of the top entry of three-level circulating absorption tower 7 and mist projection granulating tower 8, the mist projection granulating tower 8 Outlet obtains calcium chloride product.
Embodiment 2:
Present embodiments provide the collaboration extraction system of magnesium and lithium in a kind of salt lake bittern, the device of the system and its company Connect referring to embodiment 1, difference is only that: the air compressor machine 1 is piston compressor, and the cyclone separator 3 is multi-tube dusting Device, the pump is reciprocating pump.
Embodiment 3:
The collaboration extracting method of magnesium and lithium in a kind of salt lake bittern is present embodiments provided, the method uses embodiment 1 In system carry out, process flow as shown in Fig. 2, processing method the following steps are included:
It (I) is 1m by inlet amount3/ h, temperature are 30 DEG C, content of magnesium 80g/L, lithium content 4g/L, sodium content 1g/ L, chlorinity for 260g/L salt lake bittern and pressure be 0.4Mpa, temperature provides heat in natural gas for 30 DEG C of compressed air Under the conditions of enter spray roasting tower 2 and roasted, wherein compressed air and salt lake bittern volume ratio are 120:1, spray roasting tower 2 Bottom temp is 600 DEG C, and head temperature is 350 DEG C, and material is 2s, 2 top exit object of spray roasting tower in dwell time in the tower Material temperature degree is 300 DEG C, sequentially enters cyclone separator 3 and bag filter 4 is dusted processing, obtain solid material and cigarette Gas, flue-gas temperature is 250 DEG C when into bag filter 4, and flue-gas temperature is 220 DEG C when leaving bag filter 4；
(II) solid material that step (I) obtains is subjected to slurrying, countercurrent washing and is separated by filtration processing, operation temperature is 50 DEG C, obtain liquid material containing lithium and solid material containing magnesium；
(III) flue gas for obtaining step (I) carries out heat exchange with air in heat exchanger 5, into heat exchanger 5 Air temperature is 30 DEG C, and air themperature is 150 DEG C when leaving, and flue-gas temperature is 120 DEG C, and the flue gas after leaving enters neutralization and inhales Tower 7 is received, is contacted with the milk of lime that the mass concentration from calcification sizing device 6 is 5% and carries out neutralization absorption, it is molten to generate calcium chloride Liquid, tail gas qualified discharge, acquired solution enter mist projection granulating tower 8, are made by spraying with leaving the air of heat exchanger 5 as heat source Grain, obtains calcium chloride product；
(IV) solid material containing magnesium that step (II) obtains through two-stage slurrying, countercurrent washing and is separated by filtration processing again, Operation temperature is 50 DEG C, obtains magnesium hydroxide solid, gained magnesium hydroxide solid is calcined 2h under the conditions of 400 DEG C, obtains oxygen Change magnesium products；
(V) liquid material containing lithium that step (II) obtains is evaporated concentration in evaporator 16, with 120 DEG C of steaming Vapour is heat source, and condensate outlet temperature is 60 DEG C, and the solution after concentration carries out magnesium sinking reaction, reaction by precipitating reagent of sodium hydroxide Temperature be 50 DEG C, reaction time 40min, be separated by filtration under the conditions of 50 DEG C, obtained magnesium hydroxide return step (IV) into Row processing, obtained solution are again that precipitating reagent carries out sinker reaction using sodium carbonate, and reaction temperature is 50 DEG C, and the reaction time is 50min is separated by filtration under the conditions of 50 DEG C, obtains lithium carbonate product and sodium chloride solution.
To handle 1m3Salt lake bittern is foundation, and step (I) the spray roasting magnesium chloride resolution ratio is 80%, and gained is solid Body material is 200kg, is formed as shown in table 1-1.
Solid material forms after table 1-1 spray roasting
Hydrogen chloride in tail gas concentration obtained by step (III) is 5ppm, and obtaining calcium chloride product is 290kg, and calcium chloride content is 99.1wt%.
Step (II) obtains the 152kg of solid material containing magnesium, the 0.5m of liquid material containing lithium3, solution composition such as table 1-2 institute Show.
Table 1-2 liquid material containing lithium composition
Step (V) obtains concentration salting liquid 0.3m after being concentrated by evaporation3, as shown in table 1-3, magnesium sinking obtains composition after reacting To magnesium hydrate precipitate 41kg, salting liquid 0.5m3, form as shown in table 1-4, obtaining lithium carbonate product after sinker reaction is 20.35kg, carbonic acid lithium content is 97.50wt% in the product, and as shown in tables 1 to 5, then the yield of lithium is 93.8% to composition.
Salting liquid forms after table 1-3 is concentrated by evaporation
Salting liquid forms after the reaction of table 1-4 magnesium sinking
Table 1-5 lithium carbonate product composition
The 193kg of solid containing magnesium is obtained in step (IV) twice, and magnesium oxide product 133kg is obtained after calcining, oxygen in the product Change content of magnesium is 99.33wt%, is formed as shown in table 1-6, then the yield of magnesium reaches 99.1%.
Table 1-6 magnesium oxide product composition
Embodiment 4:
The collaboration extracting method of magnesium and lithium in a kind of salt lake bittern is present embodiments provided, the method uses embodiment 2 In system carry out, processing method the following steps are included:
It (I) is 1.5m by inlet amount3/ h, temperature are 40 DEG C, content of magnesium 120g/L, lithium content 6g/L, and sodium content is 2g/L, chlorinity for the salt lake bittern and pressure of 400g/L is 0.5Mpa, temperature provides for 40 DEG C of compressed air in natural gas Enter spray roasting tower 2 under heat condition to be roasted, wherein compressed air and salt lake bittern volume ratio are 100:1, spraying to roast Burning 2 bottom temp of tower is 700 DEG C, and head temperature is 450 DEG C, and material is 4s in dwell time in the tower, is gone out at the top of spray roasting tower 2 Mouthful temperature of charge is 380 DEG C, sequentially enters cyclone separator 3 and bag filter 4 is dusted processing, obtain solid material with Flue gas, flue-gas temperature is 280 DEG C when into bag filter 4, and flue-gas temperature is 250 DEG C when leaving bag filter 4；
(II) solid material that step (I) obtains is subjected to slurrying, countercurrent washing and is separated by filtration processing, operation temperature is 70 DEG C, obtain liquid material containing lithium and solid material containing magnesium；
(III) flue gas for obtaining step (I) carries out heat exchange with air in heat exchanger 5, into heat exchanger 5 Air temperature is 30 DEG C, and air themperature is 190 DEG C when leaving, and flue-gas temperature is 140 DEG C, and the flue gas after leaving enters neutralization and inhales Tower 7 is received, is contacted with the milk of lime that the mass concentration from calcification sizing device 6 is 8% and carries out neutralization absorption, it is molten to generate calcium chloride Liquid, tail gas qualified discharge, acquired solution enter mist projection granulating tower 8, are made by spraying with leaving the air of heat exchanger 5 as heat source Grain, obtains calcium chloride product；
(IV) solid material containing magnesium that step (II) obtains through two-stage slurrying, countercurrent washing and is separated by filtration processing again, Operation temperature is 70 DEG C, obtains magnesium hydroxide solid, gained magnesium hydroxide solid is calcined 1h under the conditions of 650 DEG C, obtains oxygen Change magnesium products；
(V) liquid material containing lithium that step (II) obtains is evaporated concentration in evaporator 16, with 140 DEG C of steaming Vapour is heat source, and condensate outlet temperature is 80 DEG C, and the solution after concentration carries out magnesium sinking reaction, reaction by precipitating reagent of sodium hydroxide Temperature be 70 DEG C, reaction time 25min, be separated by filtration under the conditions of 70 DEG C, obtained magnesium hydroxide return step (IV) into Row processing, obtained solution are again that precipitating reagent carries out sinker reaction using sodium carbonate, and reaction temperature is 70 DEG C, and the reaction time is 35min is separated by filtration under the conditions of 70 DEG C, obtains lithium carbonate product and sodium chloride solution.
To handle 1m3Salt lake bittern is foundation, and step (I) the spray roasting magnesium chloride resolution ratio is 85%, and gained is solid Body material is 282kg, is formed as shown in table 2-1.
Solid material forms after table 2-1 spray roasting
Hydrogen chloride in tail gas concentration obtained by step (III) is 4ppm, and obtaining calcium chloride product is 465kg, and calcium chloride content is 99.3wt%.
Step (II) obtains the 245kg of solid material containing magnesium, the 0.65m of liquid material containing lithium3, solution composition such as table 2-2 institute Show.
Table 2-2 liquid material containing lithium composition
Step (V) obtains concentration salting liquid 0.35m after being concentrated by evaporation3, it forms as shown in table 2-3, after magnesium sinking reaction To magnesium hydrate precipitate 42.8kg, salting liquid 0.5m3, as shown in Table 2-4, obtain lithium carbonate product after sinker reaction is composition 31.3kg, carbonic acid lithium content is 97.80wt% in the product, is formed as shown in table 2-5, then the yield of lithium is 96.5%.
Salting liquid forms after table 2-3 is concentrated by evaporation
Salting liquid forms after the reaction of table 2-4 magnesium sinking
Table 2-5 lithium carbonate product composition
The 287.8kg of solid containing magnesium is obtained in step (IV) twice, and magnesium oxide product 198kg is obtained after calcining, in the product Content of magnesia is 99.52wt%, is formed as shown in table 2-6, then the yield of magnesium reaches 98.5%.
Table 2-6 magnesium oxide product composition
Embodiment 5:
The collaboration extracting method of magnesium and lithium in a kind of salt lake bittern is present embodiments provided, the method uses embodiment 1 In system carry out, processing method the following steps are included:
It (I) is 2m by inlet amount3/ h, temperature are 50 DEG C, content of magnesium 150g/L, lithium content 8g/L, sodium content 2g/ L, chlorinity for 500g/L salt lake bittern and pressure be 0.6Mpa, temperature provides heat in natural gas for 50 DEG C of compressed air Under the conditions of enter spray roasting tower 2 and roasted, wherein compressed air and salt lake bittern volume ratio are 90:1, spray roasting tower 2 Bottom temp is 800 DEG C, and head temperature is 550 DEG C, and material is 6s, 2 top exit object of spray roasting tower in dwell time in the tower Material temperature degree is 450 DEG C, sequentially enters cyclone separator 3 and bag filter 4 is dusted processing, obtain solid material and cigarette Gas, flue-gas temperature is 320 DEG C when into bag filter 4, and flue-gas temperature is 280 DEG C when leaving bag filter 4；
(II) solid material that step (I) obtains is subjected to slurrying, countercurrent washing and is separated by filtration processing, operation temperature is 90 DEG C, obtain liquid material containing lithium and solid material containing magnesium；
(III) flue gas for obtaining step (I) carries out heat exchange with air in heat exchanger 5, into heat exchanger 5 Air temperature is 30 DEG C, and air themperature is 230 DEG C when leaving, and flue-gas temperature is 180 DEG C, and the flue gas after leaving enters neutralization and inhales Tower 7 is received, is contacted with the milk of lime that the mass concentration from calcification sizing device 6 is 10% and carries out neutralization absorption, generate calcium chloride Solution, tail gas qualified discharge, acquired solution enter mist projection granulating tower 8, are sprayed with leaving the air of heat exchanger 5 as heat source It is granulated, obtains calcium chloride product；
(IV) solid material containing magnesium that step (II) obtains through two-stage slurrying, countercurrent washing and is separated by filtration processing again, Operation temperature is 90 DEG C, obtains magnesium hydroxide solid, gained magnesium hydroxide solid is calcined 0.5h under the conditions of 800 DEG C, is obtained Magnesium oxide product；
(V) liquid material containing lithium that step (II) obtains is evaporated concentration in evaporator 16, with 160 DEG C of steaming Vapour is heat source, and condensate outlet temperature is 90 DEG C, and the solution after concentration carries out magnesium sinking reaction, reaction by precipitating reagent of sodium hydroxide Temperature be 90 DEG C, reaction time 10min, be separated by filtration under the conditions of 90 DEG C, obtained magnesium hydroxide return step (IV) into Row processing, obtained solution are again that precipitating reagent carries out sinker reaction using sodium carbonate, and reaction temperature is 90 DEG C, and the reaction time is 20min is separated by filtration under the conditions of 90 DEG C, obtains lithium carbonate product and sodium chloride solution.
To handle 1m3Salt lake bittern is foundation, and step (I) the spray roasting magnesium chloride resolution ratio is 90%, and gained is solid Body material is 336kg, is formed as shown in table 3-1.
Solid material forms after table 3-1 spray roasting
Hydrogen chloride in tail gas concentration obtained by step (III) is 4.2ppm, and obtaining calcium chloride product is 620kg, calcium chloride content For 99.2wt%.
Step (II) obtains the 324kg of solid material containing magnesium, the 0.6m of liquid material containing lithium3, solution composition such as table 3-2 institute Show.
Table 3-2 liquid material containing lithium composition
Step (V) obtains concentration salting liquid 0.3m after being concentrated by evaporation3, it forms as shown in table 3-3, after magnesium sinking reaction To magnesium hydrate precipitate 35.6kg, salting liquid 0.45m3, form as shown in table 3-4, obtain lithium carbonate product after sinker reaction For 42.0kg, carbonic acid lithium content is 97.92wt% in the product, and as shown in Table 3-5, then the yield of lithium is 97.3% to composition.
Salting liquid forms after table 3-3 is concentrated by evaporation
Salting liquid forms after the reaction of table 3-4 magnesium sinking
Table 3-5 lithium carbonate product composition
The 359.6kg of solid containing magnesium is obtained in step (IV) twice, and magnesium oxide product 248kg is obtained after calcining, in the product Content of magnesia is 99.60wt%, and as shown in Table 3-6, then the yield of magnesium reaches 98.8% to composition.
Table 3-6 magnesium oxide product composition
Comparative example 1:
This comparative example provides the collaboration extraction system and its processing method of magnesium and lithium in a kind of salt lake bittern, the system Device and its connection referring to embodiment 1, difference is only that: the solid outlet of the third plate and frame filter press 18 is not changed with first The top entry of plasm scouring device 11 is connected.
Its processing method is carried out referring to the method in embodiment 3, at this point, obtaining magnesium hydrate precipitate after magnesium sinking reaction cannot Back in the first slurrying wash mill 11, then mentions the magnesium hydroxide solid that magnesium unit obtains and there was only 152kg, at this time the yield of magnesium Only 78.0%.
It can be seen that collaboration extraction system comprehensive utilization wet process of the present invention and fire with comparative example based on the above embodiments Method purification technique, by the collocation and connection between each device, integrating and coupling for different process technology efficiently realizes salt The extraction of valuable element in lake bittern water, the yield of lithium reach 93% or more, and the yield of magnesium is up to 98% or more；The present invention fills simultaneously Divide and utilize fume afterheat, realizes heat cascade utilization, generated in extraction process without waste water and waste residue, tail gas qualified discharge, cleaning Environmental protection, application prospect are extensive.
The Applicant declares that the present invention is explained by the above embodiments detailed system device and process process of the invention, But the invention is not limited to above-mentioned detailed device and processes, that is, do not mean that the present invention must rely on above-mentioned detailed device and stream Cheng Caineng is implemented.It should be clear to those skilled in the art, any improvement in the present invention, to present system device With the equivalence replacement and auxiliary device of process, the addition of ingredient, the selection of concrete mode etc., protection of the invention is all fallen within Within range and the open scope.

Claims (78)

1. the collaboration extraction system of magnesium and lithium in a kind of salt lake bittern, which is characterized in that the collaboration extraction system mainly includes Spray roasting system, slurrying wash mill (9), equipment for separating liquid from solid (10), mentions magnesium unit, mentions lithium unit and cigarette dust pelletizing system Gas processing system；Wherein, the material outlet of the spray roasting system is connected with the material inlet of the dust pelletizing system, described to remove The exhanst gas outlet of dirt system is connected with the gas access of the smoke processing system, the solid matter outlet of the dust pelletizing system according to It is secondary to be connected with the slurrying wash mill (9) and equipment for separating liquid from solid (10), the solid material of the equipment for separating liquid from solid (10) Outlet is connected with the material inlet for mentioning magnesium unit, and the liquid outlet of the equipment for separating liquid from solid (10) mentions lithium unit with described Material inlet be connected, the product for mentioning magnesium unit includes magnesia, and the product for mentioning lithium unit includes that magnesium hydroxide is heavy Form sediment and lithium carbonate, the magnesium hydrate precipitate enter described in mention magnesium unit and carry out mentioning magnesium；
The smoke processing system includes neutralizing absorption tower (7) and mist projection granulating tower (8), the bottom for neutralizing absorption tower (7) Outlet is connected with the liquid inlet of mist projection granulating tower (8), and the outlet of the mist projection granulating tower (8) obtains calcium chloride product.
2. collaboration extraction system according to claim 1, which is characterized in that the spray roasting system includes air compressor machine (1) it is connected with spray roasting tower (2), the gas vent of the air compressor machine (1) with the bottom gas inlet of spray roasting tower (2).
3. collaboration extraction system according to claim 2, which is characterized in that the dust pelletizing system includes cyclone separator (3) it is connected with bag filter (4), the exhanst gas outlet of the cyclone separator (3) with the entrance of bag filter (4).
4. collaboration extraction system according to claim 3, which is characterized in that the magnesium unit that mentions includes sequentially connected One slurrying wash mill (11), the first equipment for separating liquid from solid (12), the second slurrying wash mill (13), the second equipment for separating liquid from solid (14) and calcining furnace (15), the liquid outlet of first equipment for separating liquid from solid (12) obtain sodium chloride solution, and described second is solid The liquid outlet of liquid separating apparatus (14) is connected with the top entry of the first slurrying wash mill (11), and described second is separated by solid-liquid separation The solid outlet of device (14) is connected with the entrance of calcining furnace (15).
5. collaboration extraction system according to claim 4, which is characterized in that the lithium unit that mentions includes sequentially connected steaming Send out device (16), the first settler (17), third equipment for separating liquid from solid (18), the second settler (19) and the 4th separation of solid and liquid Device (20), evaporator (16) condensate outlet are connected with the top entry of the second slurrying wash mill (13), and described The solid outlet of three equipment for separating liquid from solid (18) is connected with the top entry of the first slurrying wash mill (11), the 4th solid-liquid It is also connected with after separator (20) conveyer (21), the liquid outlet of the 4th equipment for separating liquid from solid (20) obtains sodium chloride Solution.
6. collaboration extraction system according to claim 5, which is characterized in that the bottom inlet of the spray roasting tower (2) Before, between slurrying wash mill (9) and equipment for separating liquid from solid (10), the first slurrying wash mill (11) is separated by solid-liquid separation with first and fills Set between (12), between the second slurrying wash mill (13) and the second equipment for separating liquid from solid (14), the first settler (17) with Pump is equipped between the second settler (19) and the 4th equipment for separating liquid from solid (20) between third equipment for separating liquid from solid (18).
7. collaboration extraction system according to claim 2, which is characterized in that the air compressor machine (1) is screw compressor Or piston compressor.
8. collaboration extraction system according to claim 3, which is characterized in that the cyclone separator (3) includes single tube rotation Wind deduster and/or multi-tube dust cleaner.
9. collaboration extraction system according to claim 5, which is characterized in that the equipment for separating liquid from solid (10), first are consolidated Liquid separating apparatus (12), the second equipment for separating liquid from solid (14), third equipment for separating liquid from solid (18) and the 4th equipment for separating liquid from solid It (20) is filter device or centrifugal device.
10. collaboration extraction system according to claim 9, which is characterized in that the equipment for separating liquid from solid (10), first are consolidated Liquid separating apparatus (12), the second equipment for separating liquid from solid (14), third equipment for separating liquid from solid (18) and the 4th equipment for separating liquid from solid It (20) is plate and frame filter press.
11. collaboration extraction system according to claim 5, which is characterized in that the evaporator (16) is the steaming of triple effect falling liquid film Send out device.
12. collaboration extraction system according to claim 6, which is characterized in that the pump is centrifugal pump, reciprocating pump, rotation Pump or peripheral pump in any one or at least two combination.
13. collaboration extraction system according to claim 3, which is characterized in that the smoke processing system further includes hot friendship Parallel operation (5) and calcification sizing device (6), the thermal fluid inlet of the heat exchanger (5) and the flue gas of the bag filter (4) Outlet is connected, and the hot fluid outlet ports of the heat exchanger (5) are connected with the bottom gas inlet for neutralizing absorption tower (7), institute The outlet for stating calcification sizing device (6) is connected with the bottom slurry import for neutralizing absorption tower (7).
14. collaboration extraction system according to claim 1, which is characterized in that the neutralization absorption tower (7) and mist projection granulating Circulating pump is equipped between tower (8), the entrance of the circulating pump is connected with the outlet at bottom for neutralizing absorption tower (7), described to follow The outlet of ring pump is connected with the liquid inlet of the top entry and mist projection granulating tower (8) that neutralize absorption tower (7).
15. collaboration extraction system according to claim 13, which is characterized in that the heat exchanger (5) is changed for shell and tube Hot device.
16. collaboration extraction system according to claim 14, which is characterized in that the neutralization absorption tower (7) is followed for three-level Ring absorption tower.
17. collaboration extraction system according to claim 14, which is characterized in that the circulating pump be centrifugal pump, reciprocating pump, Any one in rotary pump or peripheral pump.
18. the processing method of collaboration extraction system described in one of -17 according to claim 1, which is characterized in that the method packet Include following steps:
(a) salt lake bittern is subjected to spray roasting, then obtains solid material and flue gas through dust removal process；
(b) solid material that step (a) obtains is subjected to slurrying washing and obtains liquid material containing lithium after being separated by solid-liquid separation and contains magnesium Solid material；
(c) solid material containing magnesium that step (b) obtains is obtained into magnesium hydroxide solid through multipolarity plasm scouring and after being separated by solid-liquid separation, Magnesia is obtained through calcining again；
(d) liquid material containing lithium that step (b) obtains successively is concentrated by evaporation, obtained after multi stage precipitation reaction and separation of solid and liquid Magnesium hydroxide and lithium carbonate handle obtained magnesium hydroxide return step (c)；
The flue gas that step (a) is obtained is handled, processing method the following steps are included:
(A) flue gas for obtaining step (a) carries out neutralization absorption after heat exchange, obtains calcium chloride solution, tail gas qualified discharge；
(B) calcium chloride solution that step (A) obtains is obtained into calcium chloride product through mist projection granulating.
19. according to the method for claim 18, which is characterized in that step (a) salt lake bittern refer to through extraction potassium, After sodium and bromine based on magnesium chloride, the solution containing lithium chloride and sodium chloride, wherein content of magnesium be 80-150g/L, chlorinity For 260-500g/L, lithium content 4-8g/L, sodium content 1-2g/L.
20. according to the method for claim 18, which is characterized in that step (a) the salt lake bittern feeding temperature is 30-50 ℃。
21. according to the method for claim 18, which is characterized in that it is empty that step (a) the spray roasting needs are passed through compression Gas, the compressed air are provided by air compressor machine (1).
22. according to the method for claim 21, which is characterized in that the compressed air pressure is 0.4-0.6MPa, air inlet Temperature is 30-50 DEG C.
23. according to the method for claim 21, which is characterized in that the compressed air is (90- with salt lake bittern volume ratio 120):1。
24. according to the method for claim 18, which is characterized in that step (a) spray roasting provides heat in fuel Under the conditions of carry out.
25. according to the method for claim 24, which is characterized in that the fuel is methanol, diesel oil, liquefied gas or natural gas In any one.
26. according to the method for claim 18, which is characterized in that step (a) spray roasting is in spray roasting tower (2) Interior progress.
27. according to the method for claim 26, which is characterized in that spray roasting tower (2) bottom temp is 600-800 DEG C, head temperature is 350-550 DEG C.
28. according to the method for claim 26, which is characterized in that the interior residence time of material of the spray roasting tower (2) is 2-6s。
29. according to the method for claim 28, which is characterized in that the interior residence time of material of the spray roasting tower (2) is 3-5s。
30. according to the method for claim 26, which is characterized in that spray roasting tower (2) outlet mass temperatures are 300-500℃。
31. according to the method for claim 18, which is characterized in that step (a) dust removal process is respectively in cyclonic separation It is carried out in device (3) and bag filter (4).
32. according to the method for claim 31, which is characterized in that bag filter (4) input gas temperature is 220-320℃。
33. according to the method for claim 32, which is characterized in that bag filter (4) input gas temperature is 250-300℃。
34. according to the method for claim 31, which is characterized in that bag filter (4) exit gas temperature is 200-300℃。
35. according to the method for claim 34, which is characterized in that bag filter (4) exit gas temperature is 220-280℃。
36. according to the method for claim 18, which is characterized in that step (b) and step (c) washing are washed for adverse current It washs.
37. according to the method for claim 18, which is characterized in that step (b) and step (c) are described to be separated by solid-liquid separation as filtering Separation.
38. according to the method for claim 18, which is characterized in that step (b) and step (c) the slurrying washing and solid-liquid Lock out operation temperature is 50-90 DEG C.
39. according to the method for claim 38, which is characterized in that step (b) and step (c) the slurrying washing and solid-liquid Lock out operation temperature is 60-80 DEG C.
40. according to the method for claim 18, which is characterized in that step (c) the multipolarity plasm scouring and separation of solid and liquid It washs and is separated by solid-liquid separation for two-stage slurrying.
41. according to the method for claim 18, which is characterized in that step (c) calcining carries out in calcining furnace (15).
42. according to the method for claim 18, which is characterized in that step (c) calcination temperature is 400-800 DEG C.
43. according to the method for claim 42, which is characterized in that step (c) calcination temperature is 550-750 DEG C.
44. according to the method for claim 43, which is characterized in that step (c) calcination temperature is 600-700 DEG C.
45. according to the method for claim 18, which is characterized in that step (c) calcination time is 0.5-2h.
46. according to the method for claim 45, which is characterized in that step (c) calcination time is 0.8-1.2h.
47. according to the method for claim 18, which is characterized in that content of magnesia in step (c) magnesium oxide product Greater than 98wt%.
48. according to the method for claim 18, which is characterized in that step (d) is described to be concentrated by evaporation in evaporator (16) It carries out.
49. according to the method for claim 18, which is characterized in that step (d) evaporation and concentration is using steam as heat source.
50. according to the method for claim 49, which is characterized in that 120-160 DEG C of the inlet steam temperature.
51. according to the method for claim 50, which is characterized in that the inlet steam temperature is 130-150 DEG C.
52. according to the method for claim 49, which is characterized in that the steam condensate outlet temperature is 60-90 DEG C.
53. method according to claim 52, which is characterized in that the steam condensate outlet temperature is 70-80 DEG C.
54. according to the method for claim 18, which is characterized in that step (d) the multi stage precipitation reaction and separation of solid and liquid Respectively level-one precipitation reaction and separation of solid and liquid and two-stage precipitation reaction and separation of solid and liquid.
55. method according to claim 54, which is characterized in that the level-one precipitation reaction is magnesium sinking reaction, with hydrogen-oxygen Change sodium is precipitating reagent.
56. method according to claim 54, which is characterized in that the level-one precipitation reaction temperature is 50-90 DEG C.
57. method according to claim 56, which is characterized in that the level-one precipitation reaction temperature is 60-80 DEG C.
58. method according to claim 54, which is characterized in that the level-one precipitation reaction time is 10-40min.
59. method according to claim 54, which is characterized in that the two-stage precipitation reaction is that sinker reacts, with carbonic acid Sodium is precipitating reagent.
60. method according to claim 54, which is characterized in that the two-stage precipitation reaction temperature is 50-90 DEG C.
61. method according to claim 60, which is characterized in that the two-stage precipitation reaction temperature is 60-80 DEG C.
62. method according to claim 54, which is characterized in that the precipitation reaction time described in the second level is 20- 50min。
63. method according to claim 54, which is characterized in that step (d) is described to be separated by solid-liquid separation to be separated by filtration, and is operated Temperature is 50-90 DEG C.
64. method according to claim 63, which is characterized in that step (d) is described to be separated by solid-liquid separation to be separated by filtration, and is operated Temperature is 60-80 DEG C.
65. according to the method for claim 18, which is characterized in that step (A) described heat exchange is using air as cold source.
66. according to the method for claim 18, which is characterized in that air themperature is 150- after step (A) described heat exchange 230℃。
67. method according to claim 66, which is characterized in that air themperature is 170- after step (A) described heat exchange 210℃。
68. according to the method for claim 18, which is characterized in that flue-gas temperature is 120- after step (A) described heat exchange 180℃。
69. method according to claim 68, which is characterized in that flue-gas temperature is 130- after step (A) described heat exchange 150℃。
70. according to the method for claim 18, which is characterized in that step (A) neutralization absorbs in and absorption tower (7) Interior progress.
71. according to the method for claim 18, which is characterized in that it is to neutralize that step (A) neutralization, which is absorbed with milk of lime, Agent, mass concentration 5%-10%.
72. method according to claim 71, which is characterized in that the milk of lime is handled by lime and water through slurrying It arrives.
73. the method according to claim 72, which is characterized in that slurrying processing in calcification sizing device (6) into Row.
74. according to the method for claim 18, which is characterized in that step (A) the hydrogen chloride in tail gas content is not more than 10ppm。
75. method according to claim 74, which is characterized in that step (A) the hydrogen chloride in tail gas content is not more than 5ppm。
76. according to the method for claim 18, which is characterized in that step (B) mist projection granulating is in mist projection granulating tower (8) Interior progress.
77. according to the method for claim 18, which is characterized in that step (B) mist projection granulating is with step (A) heat exchange Air afterwards is heat source.
78. method described in one of 8-77 according to claim 1, which is characterized in that the described method comprises the following steps:
(I) the temperature salt lake bittern for being 30-50 DEG C and pressure is 0.4-0.6MP a, temperature is 30-50 DEG C compressed air are existed Fuel is provided and is roasted under heat condition into spray roasting tower (2), and wherein compressed air is with salt lake bittern volume ratio (90-120): 1, spray roasting tower (2) bottom temp is 600-800 DEG C, and head temperature is 350-550 DEG C, and material stops in tower Stay the time be 3-5s, spray roasting tower (2) top exit temperature of charge be 300-500 DEG C, sequentially enter cyclone separator (3) and Bag filter (4) is dusted processing, obtains solid material and flue gas, and flue-gas temperature is when into bag filter (4) 250-300 DEG C, flue-gas temperature is 220-280 DEG C when leaving bag filter (4)；
(II) solid material that step (I) obtains is subjected to slurrying, countercurrent washing and is separated by filtration processing, operation temperature 60- 80 DEG C, obtain liquid material containing lithium and solid material containing magnesium；
(III) flue gas for obtaining step (I) carries out heat exchange with air in heat exchanger (5), when leaving heat exchanger (5) Air themperature is 170-210 DEG C, and flue-gas temperature is 130-150 DEG C, and the flue gas after leaving, which enters, neutralizes absorption tower (7), and is come from The milk of lime contact that the mass concentration of calcification sizing device (6) is 5-10% carries out neutralization absorption, and emptying hydrogen chloride in tail gas is dense Degree is not higher than 5ppm, and acquired solution enters mist projection granulating tower (8), is sprayed with leaving the air of heat exchanger (5) as heat source It is granulated, obtains calcium chloride product；
(IV) solid material containing magnesium that step (II) obtains through two-stage slurrying, countercurrent washing and is separated by filtration processing again, operated Temperature is 60-80 DEG C, obtains magnesium hydroxide solid, gained magnesium hydroxide solid is calcined 0.8- under the conditions of 600-700 DEG C 1.2h obtains the high-purity magnesium oxide that content of magnesia is greater than 98%；
(V) liquid material containing lithium that step (II) obtains is evaporated concentration in evaporator (16), with 130-150 DEG C Steam is heat source, and the solution after concentration carries out magnesium sinking reaction by precipitating reagent of sodium hydroxide, and reaction temperature is 60-80 DEG C, reaction Time is 10-40min, is separated by filtration under the conditions of 60-80 DEG C, and obtained magnesium hydroxide return step (IV) is handled, and is obtained The solution arrived carries out sinker reaction by precipitating reagent of sodium carbonate again, and reaction temperature is 60-80 DEG C, reaction time 20-50min, It is separated by filtration under the conditions of 60-80 DEG C, obtains lithium carbonate product and sodium chloride solution.
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