CN103896296B - A kind of air supporting polymkeric substance is from the method and apparatus of salt lake brine boron extraction - Google Patents
A kind of air supporting polymkeric substance is from the method and apparatus of salt lake brine boron extraction Download PDFInfo
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- CN103896296B CN103896296B CN201410101295.1A CN201410101295A CN103896296B CN 103896296 B CN103896296 B CN 103896296B CN 201410101295 A CN201410101295 A CN 201410101295A CN 103896296 B CN103896296 B CN 103896296B
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Abstract
The invention discloses the method and apparatus of a kind of air supporting polymkeric substance from salt lake brine boron extraction.The method comprising the steps of: be filled to by salt lake brine in air supporting column extractor, bubble is blasted from air supporting column extractor lower end, the water-soluble polymers aqueous solution is added from air supporting column extractor sidewall U-shaped thrust-augmenting nozzle, aqueous solutions of polymers mixes with the salt lake brine of overflow in U-shaped thrust-augmenting nozzle, gained mixing solutions enters in air supporting column extractor through charging ring spray, collected the foam produced above air supporting column extractor by scraper plate, the boron in foam is reclaimed in back extraction.The method utilizes air supporting column extractor to complete, and described air supporting column extractor comprises hollow cylinder, gas feed, gas distributor, charging ring, the U-shaped thrust-augmenting nozzle being positioned at hollow cylinder outer side wall, the import of the water-soluble polymers aqueous solution and froth paddle.The present invention utilizes water-soluble polymers in salt lake brine, form polymer molecule microscopic aggregates trapping boron, and then air supporting trapping boron-containing polymer molecule microscopic aggregates, is suitable for all types of salt lake brine and carries boron.
Description
Technical field
The invention belongs to salt lake brine and put forward boron technical field, be specifically related to the method and apparatus of a kind of air supporting polymkeric substance from salt lake brine boron extraction.
Background technology
Boron is one of rare elements important in the earth's crust, because its insulation heatproof antifriction flame retardant properties is in the material more excellent and be widely used in each department of national economy.China's boron resource is abundanter, but the boron magnesium ore deposit (white boron) that wherein can utilize or be easy to process only accounts for 6.7% of domestic reserves.Along with the continuous expansion of boron Application Areas, from boron rock, only extract the demand that boron can not meet market far away, therefore develop other available boron resources significant.Be richly stored with in the western salt lake of China boron resource.From salt lake brine, carry boron can realize salt lake resources comprehensive utilization, promote salt lake sustainable development of chemical industry.At present, the method carrying boron from salt lake brine has: substep acid precipitation method, adsorption coprecipitation method, ion exchange method and solvent extration etc.Wherein Recovery by Solvent Extraction Methold boron has the advantages such as selectivity is good, product purity is high, the rate of recovery is high, easy and simple to handle, equipment is simple, and extraction process running cost is low, starting material less energy consumption, without the three wastes, compare additive method and have clear superiority.
From salt lake brine, boron extraction adopts alcohol type organic to be extraction agent usually, boron is extracted other Component seperation in organic mutual-assistance itself and bittern.Both at home and abroad the boron extraction method of open report mainly contains three kinds: be 1. organic extractant with water-fast monohydroxy-alcohol, extract rare boric acid aqueous solution, then obtain boric acid solution by water reextraction organic phase with physical dissolution method, then carries out concentratedly separating out boric acid; 2. use 1,3-dibasic alcohol to be organic extractant, react generate neutral ester with boron, the ester then decomposed in organic phase with alkaline aqueous solution obtains sodium metaborate, forms boric acid finally by acidification; 3. in alkaline medium, the derivatives reaction of boron and pyrocatechol and saligenol etc. generates complexing borate, then analyses organic phase with acidolysis and obtain boric acid.In oneself disclosed alcohols extraction boron system, unitary fatty alcohol (as 2-Ethylhexyl Alcohol) is widely used.But unitary fatty alcohol and boric acid form chain ester class, the cyclic ester class formed not as binary aliphatic alcohol and boric acid is stablized, and binary aliphatic alcohol has than unitary fatty alcohol more preferably carries effect of boron and lower water-soluble.Have 1 of 8 ~ 9 carbon atoms at present, 3 dibasic alcohol (as 2-ethyl-1,3-hexylene glycol) be generally acknowledged there is higher boron partition ratio carry boron extraction agent.The organic mixture obtained after different alcohol kind of extractants mixes by a certain percentage also there is open report as carrying boron extraction agent, such as by monohydroxy-alcohol and monohydroxy-alcohol, monohydroxy-alcohol mixes with dibasic alcohol, both advantages can be utilized simultaneously, while raising boron percentage extraction, reduce the solution loss of extraction process organic extractant in aqueous salt brine.The patent CN101676206 alcohol mixture that a kind of 2-ethyl-1,3-hexylene glycol combines with isooctyl alcohol, primary isoamyl alcohol respectively of having reported for work puies forward the method extracting boron after lithium bittern from salt lake.Patent US3741731 is dissolved in boron extraction in kerosene after adopting derivatives of salicyl alcohol to mix with primary isoamyl alcohol.
The extraction agent extracting boron at present from salt lake brine is all organic alcohols extraction agent, and the weak point of this kind of extractants is, the pH scope that extraction system is suitable for is not wide.Fatty alcohol has good effect of extracting in an acidic solution, and aromatic alcohol has higher partition ratio in the basic conditions, cannot adapt to the requirement that salt lake brine extracts under neutrality, weak acid or weak base condition.In addition, in actual application, alcohol type organic is volatile, threatens to operator ' s health.
Air supporting extraction refers to and blast bubble in oil water two phase system, take bubble as carrier, and the target substance in trapping aqueous phase, promotes that it is to oil phase mass transfer.Patent CN102154563A reports the method for a kind of air supporting extraction Lithium from Salt Lake Brine, and the method oil phase adopts the kerosin of TRI N BUTYL PHOSPHATE, take iron trichloride as synergist.Patent CN102895803A report a kind of small molecules Organic Alcohol and inorganic salt solution composition double-aqueous phase system in blast bubble, be carrier with bubble, floating and enriching and fractionate aqueous solutions trace amount chloramphenicol.Also there is the open report about pneumatic flotation in technics of metallurgy mineral dressing field.Solid mineral is first fine into after particle through pulverizing grinder and is distributed in the aqueous solution, then adds water soluble surfactant active's (also known as collecting agent) in aqueous.Because the various mineral surface hydrophilic and hydrophobics in raw ore differ, tensio-active agent can be adsorbed on the ore particle surface with certain mineral surface-active.When blasting bubble in the mixing solutions of ore particle and water, the ore particle of coated tensio-active agent by bubble trap, can rise with bubble, thus with other minerals separation.Patent CN101091935 reports a kind of collecting agent combined by the ethyl xanthogenate of 60 ~ 80% and the thiourethanes of 20 ~ 40%, and it is strong to the collecting ability of zink sulphide, selectivity good, can obtain higher-grade zinc ore concentrate after pneumatic flotation; Patent CN101716559A proposes a kind of organic compound benzyl hydroximic acid for the ore deposit flotation of bertrandite class beryllium, can significantly improve containing beryllium Floatation Concentrate Grade.But the air supporting extracting process in prior art all can not realize boron extraction from salt lake brine effectively.
Summary of the invention
For the problem of prior art, an object of the present invention is a kind of method providing air supporting polymkeric substance from salt lake brine boron extraction, realizes extraction and isolation boron from salt lake brine.
In order to achieve the above object, present invention employs following technical scheme:
Air supporting polymkeric substance is from a method for salt lake brine boron extraction, and described method comprises the steps:
Salt lake brine containing boron is mixed with the water-soluble polymers aqueous solution in air supporting column extractor outer side wall U-shaped thrust-augmenting nozzle and contacts, Water-soluble Polymer Molecules salt condensation for removing water in salt lake brine is made to form polymer molecule microscopic aggregates, gained mixing solutions enters in air supporting column extractor through charging ring spray, the polymer molecule microscopic aggregates having trapped boron adsorbs at bubble surface, taken away by rising bubble, collect the foam produced in air supporting column extractor upper end, the boron in foam is reclaimed in back extraction.
Principle of the present invention is: water-soluble polymers salt condensation for removing water in salt lake brine forms polymer molecule microscopic aggregates.The active group come out after boron in salt lake brine and aggregate molecule segment dewater interacts, and is aggregated body trapping.Because water-soluble polymers has surfactivity, when blasting bubble in salt lake brine, the polymer molecule microscopic aggregates having trapped boron adsorbs at bubble surface, comes air supporting column extractor upper end with rising bubble, collect the foam produced in air supporting column extractor upper end, the boron in foam is reclaimed in back extraction.
Preferably, described method comprises the steps:
(1) Salt lake brine containing boron is filled in air supporting column extractor;
(2) pump into gas from air supporting column extractor lower end, adjustment pump airshed makes the gas pumped into be that air bubbles dispersion phase form is dispersed in salt lake brine;
(3) the water-soluble polymers aqueous solution is pumped into from air supporting column extractor outer side wall U-shaped thrust-augmenting nozzle, aqueous solutions of polymers at room temperature mixes with the salt lake brine of overflow and contacts in U-shaped thrust-augmenting nozzle, Water-soluble Polymer Molecules salt condensation for removing water in salt lake brine is made to form polymer molecule microscopic aggregates, gained mixing solutions enters in air supporting column extractor through charging ring spray, the polymer molecule microscopic aggregates having trapped boron adsorbs at bubble surface, is taken away by rising bubble;
(4) collect the foam produced in air supporting column extractor upper end, the boron in foam is reclaimed in back extraction.
Preferably, in described Salt lake brine containing boron the concentration of boron with B
2o
3meter, its mass percentage concentration is 0.01 ~ 3%, such as 0.03%, 0.06%, 0.1%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6% or 2.8%, be preferably 0.3 ~ 3%.
Preferably, step (2) described gas is selected from the combination of any one or at least two kinds in air, nitrogen or rare gas element.
The present invention, for realizing air floatation boron from salt lake brine, must control the water-soluble polymers that corresponding operating condition makes to add and in salt lake brine, form polymer molecule microscopic aggregates in advance.If aggregate cannot be formed, then the boron in salt lake brine cannot by bubble trap, this is because the polymer molecule segment of boron in salt lake brine and aquation interacts very weak.But, after when polymer molecule, in salt lake brine, salt condensation for removing water forms aggregate, the dehydration of aggregate surface polymer molecule segment makes active group come out, and the active group of boron and aggregate molecule segment interacts, thus is aggregated body trapping.Aggregate quantity of formation, synthesis speed, and it is determined the collection efficiency of boron in salt lake brine by the speed that bubble absorption traps.Pump into flow by what control the water-soluble polymers aqueous solution, quantity and speed that water-soluble polymers salt condensation for removing water in salt lake brine forms microscopic aggregates can be controlled, thus control the speed of polymkeric substance microcosmic molecule aggregates extraction trapping boron; By controlling air-blowing speed, Air Bubble Size and gas holdup can be controlled, thus control the quantity of the boron-containing polymer molecule microscopic aggregates that can be trapped by bubble absorption in the unit time.
Preferably, the described gas flow that pumps into is 0.1 ~ 100mL/min, be such as 1mL/min, 5mL/min, 10mL/min, 15mL/min, 20mL/min, 25mL/min, 30mL/min, 35mL/min, 40mL/min, 45mL/min, 50mL/min, 55mL/min, 60mL/min, 65mL/min, 70mL/min, 75mL/min, 80mL/min, 85mL/min, 90mL/min or 95mL/min, be preferably 0.1 ~ 20mL/min.
The speed that pumps into of the described water-soluble polymers aqueous solution of step (3) is 0.01 ~ 5mL/min, 0.3mL/min, 0.5mL/min, 0.7mL/min, 0.9mL/min, 1.1mL/min, 1.3mL/min, 1.5mL/min, 1.7mL/min, 1.9mL/min, 2.1mL/min, 2.3mL/min, 2.5mL/min, 2.7mL/min, 2.9mL/min, 3.1mL/min, 3.3mL/min, 3.5mL/min, 3.7mL/min, 3.9mL/min, 4.1mL/min, 4.3mL/min, 4.5mL/min or 4.7mL/min, be preferably 0.01 ~ 2mL/min.
Preferably, described water-soluble polymers is polyoxyethylene glycol (PEG), polypropylene glycol, methoxy poly (ethylene glycol) (MPEG), methoxyl group polypropylene glycol, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), PLURONIC F-127, polyox-yethylene-polyoxypropylene block copolymer, PEP-101 (EOPO), polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, polypropylene glycol-polyoxyethylene glycol-mono—n—butylester triblock copolymer, the mixture of any one or at least two kinds in methylcellulose gum or Natvosol, preferably water dissolubility amphiphilic block copolymer, further preferred PLURONIC F-127, polyox-yethylene-polyoxypropylene block copolymer, PEP-101 (EOPO), the mixture of any one or at least two kinds in polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer or polypropylene glycol-polyoxyethylene glycol-mono—n—butylester triblock copolymer.
Be 100 listed as parts by weight with the water-soluble polymers aqueous solution, the amount of polymkeric substance is 8 ~ 80 weight parts, such as 10 weight parts, 14 weight parts, 18 weight parts, 22 weight parts, 26 weight parts, 30 weight parts, 34 weight parts, 38 weight parts, 42 weight parts, 46 weight parts, 50 weight parts, 54 weight parts, 58 weight parts, 62 weight parts, 66 weight parts, 70 weight parts, 74 weight parts or 78 weight parts, be preferably 30 ~ 80 weight parts.
The add-on of the described water-soluble polymers aqueous solution calculates with the weight percentage of the add-on of described Salt lake brine containing boron: be 100 parts by weight with Salt lake brine containing boron, the add-on of the described water-soluble polymers aqueous solution is 0.5 ~ 80 weight part, such as 1 weight part, 3 weight parts, 5 weight parts, 7 weight parts, 9 weight parts, 10 weight parts, 14 weight parts, 18 weight parts, 22 weight parts, 26 weight parts, 30 weight parts, 34 weight parts, 38 weight parts, 42 weight parts, 46 weight parts, 50 weight parts, 54 weight parts, 58 weight parts, 62 weight parts, 66 weight parts, 70 weight parts, 74 weight parts or 78 weight parts, be preferably 0.5 ~ 10 weight part.
Employing is scraped bubble method and is collected foam, namely adopts the foam that scraper plate scraping air supporting column extractor upper port produces.
Preferably, the boron in reverse-extraction agent back extraction recovery foam is made with hydrochloric acid.
Two of object of the present invention is the device providing a kind of air supporting polymkeric substance from salt lake brine boron extraction, and described device is air supporting column extractor; Described air supporting column extractor comprises hollow cylinder, is provided with gas feed, is provided with gas distributor above gas feed bottom it, its role is to dispersed bubble; An annular, the tapered opening in inner side, the inner charging ring for cavity structure is provided with above gas distributor; Hollow cylinder outer side wall is provided with U-shaped thrust-augmenting nozzle, and its lower port is communicated with along the tangential direction of charging ring with charging ring; The hollow cylinder at the upper port place of U-shaped thrust-augmenting nozzle is provided with diversion trench; Described U-shaped thrust-augmenting nozzle is provided with the import of the water-soluble polymers aqueous solution, and the position of described water-soluble polymers aqueous solution import and the vertical range of charging ring are 1/20 ~ 1/10 of hollow cylinder height; The top of described hollow cylinder is provided with the enlarging district of top seal, and the sidewall in enlarging district is provided with foam outlet.
Air supporting polymkeric substance of the present invention preferably adopts air supporting polymkeric substance as above to realize from the device of salt lake brine boron extraction from the method for salt lake brine boron extraction.
The position of described water-soluble polymers aqueous solution import and the vertical range of charging ring are 1/20 ~ 1/10 of hollow cylinder height, such as 1/19,1/18,1/17,1/16,1/15,1/14,1/13,1/12 or 1/11, its role is to the polymer molecule microscopic aggregates forming some amount in the mixing liquid ensureing to flow into charging annular space chamber.
Preferably, be provided with froth paddle in described enlarging district, it is with driven by motor.
Preferably, described hollow cylinder upper end, near place of enlarging district, is provided with salt lake brine opening for feed, and hollow cylinder lower end is provided with salt lake brine outlet below charging ring, above gas distributor.
Preferably, the height of described hollow cylinder is 2 ~ 10 meters, and aspect ratio is 10:1 ~ 100:1, is preferably 20:1 ~ 50:1.
Air supporting polymkeric substance of the present invention is as follows from the working process of the device (i.e. air supporting column extractor) of salt lake brine boron extraction:
First, Salt lake brine containing boron is filled in the hollow cylinder of air supporting column extractor by salt lake brine opening for feed.Then, pump into gas from gas feed, by gas distributor, bubble is dispersed in salt lake brine.The water-soluble polymers aqueous solution is pumped in U-shaped thrust-augmenting nozzle by the import of the water-soluble polymers aqueous solution, the salt lake brine being entered U-shaped thrust-augmenting nozzle by diversion trench overflow and the water-soluble polymers aqueous solution are mixed at the lower semisection of U-shaped thrust-augmenting nozzle and contact, and water-soluble polymers salt condensation for removing water in salt lake brine forms polymer molecule microscopic aggregates.The mixing solutions obtained after the water-soluble polymers aqueous solution mixes with salt lake brine enters charging ring by the lower port of U-shaped thrust-augmenting nozzle along the tangential direction of charging ring, the mixing solutions flowing into charging annular space chamber is after ring body cavity buffering, and from the inner side of charging ring, tapered opening ejection enters hollow cylinder.The polymer molecule microscopic aggregates having trapped boron adsorbs at bubble surface, is taken away enter enlarging district by rising bubble.In enlarging district, collect by the froth paddle of driven by motor the foam produced, the boron in the foam of being discharged by foam outlet is reclaimed in back extraction, discharges finally by salt lake brine outlet the salt lake brine having carried boron.
Compared with the prior art, the present invention has following beneficial effect:
(1) the present invention utilizes water-soluble polymers in salt lake brine, form polymer molecule microscopic aggregates trapping boron, and then air supporting trapping boron-containing polymer molecule microscopic aggregates, does not need to use organic extractant.In salt lake brine, the collection efficiency of boron depends on aggregate quantity of formation, synthesis speed and its speed trapped by bubble absorption, artificially controlled.Described method and device can be applicable to the extraction of boron in the salt lake brine containing lower boron concentration.And air supporting process only needs to add a small amount of water-soluble polymers, and the loss of polymkeric substance in raffinate is less than 0.3%.
(2) the present invention is by the polymer molecule microscopic aggregates in air supporting trapping salt lake brine, completes the extracting and enriching to boron in salt lake brine.Different from traditional air supporting extracting operation, boron method of carrying of the present invention does not need to build two-phase coexistent system in advance, different from conventional foam floatable minerals yet, can water-soluble target substance in the direct flotation concentration and separation aqueous solution.
(3) method boron rate of extraction of the present invention is fast, and single-stage extraction rate can reach 80%, and the high molecular polymer of interpolation is after boron is wherein reclaimed in air supporting trapping, back extraction, reusable.And described air supporting extraction can be carried out under neutrality or solutions of weak acidity, and pH value of solution subject range is wide.
(4) the method can be applicable to chloride type, sulfate type, all kinds of salt lake brine of carbonate type, and not by the impact of potassium, sodium, calcium, magnesium, lithium concentration in dissimilar salt lake brine, can realize being separated and enrichment boron from the high salt lake brine of saltiness, strong adaptability.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of air supporting polymkeric substance from salt lake brine boron extraction;
Fig. 2 is charging ring vertical view;
Fig. 3 is charging ring A-A position sectional view.
Figure of description mark is as follows:
1 is gas feed, and 2 is gas distributor, and 3 is salt lake brine outlet, 4 is charging ring, and 5 is the import of the water-soluble polymers aqueous solution, and 6 is U-shaped thrust-augmenting nozzle, 7 is hollow cylinder, and 8 is diversion trench, and 9 is enlarging district, 10 is froth paddle, 11 is motor, and 12 is foam outlet, and 13 is salt lake brine opening for feed, 14 is the tapered opening in inner side, and h is the vertical range of the import of the water-soluble polymers aqueous solution and charging ring.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in more detail.But following example is only simple and easy example of the present invention, and do not represent or limit the scope of the present invention, protection scope of the present invention is as the criterion with claims.
Air supporting polymkeric substance is from a device for salt lake brine boron extraction, and described device is air supporting column extractor; Described air supporting column extractor comprises hollow cylinder 7, is provided with gas feed 1 bottom it, is provided with gas distributor 2 above gas feed 1.An annular, the tapered opening 14 in inner side, the inner charging ring 4 for cavity structure is provided with above gas distributor 2; Hollow cylinder 7 outer side wall is provided with U-shaped thrust-augmenting nozzle 6, and its lower port is communicated with along the tangential direction of charging ring 4 with charging ring 4; The hollow cylinder 7 at the upper port place of U-shaped thrust-augmenting nozzle 6 is provided with diversion trench 8; Water-soluble polymers aqueous solution import 5 is communicated with U-shaped thrust-augmenting nozzle 6, and the position of described water-soluble polymers aqueous solution import 5 and the vertical range of charging ring 4 are 1/20 ~ 1/10 of hollow cylinder 7 height.The top of described hollow cylinder 7 is provided with the enlarging district 9 of top seal, and the sidewall in enlarging district 9 is provided with foam outlet 12.Be provided with froth paddle 10 in described enlarging district 9, it drives with motor 11.Described hollow cylinder 7 upper end, near place of enlarging district 9, is provided with salt lake brine opening for feed 13, and hollow cylinder 7 lower end is provided with salt lake brine outlet 3 below charging ring 4, above gas distributor 2.The height of described hollow cylinder 7 is 2 ~ 10 meters, and aspect ratio is 10:1 ~ 100:1, is preferably 20:1 ~ 50:1.
Air supporting polymkeric substance of the present invention is as follows from the working process of the device (i.e. air supporting column extractor) of salt lake brine boron extraction:
First, Salt lake brine containing boron is filled in the hollow cylinder 7 of air supporting column extractor by salt lake brine opening for feed 13.Then, pump into gas from gas feed 1, by gas distributor 2, bubble is dispersed in salt lake brine.The water-soluble polymers aqueous solution is pumped in U-shaped thrust-augmenting nozzle 6 by water-soluble polymers aqueous solution import 5, the salt lake brine being entered U-shaped thrust-augmenting nozzle 6 by diversion trench 8 overflow and the water-soluble polymers aqueous solution are mixed at the lower semisection of U-shaped thrust-augmenting nozzle 6 and contact, and water-soluble polymers salt condensation for removing water in salt lake brine forms polymer molecule microscopic aggregates.The mixing solutions obtained after the water-soluble polymers aqueous solution mixes with salt lake brine enters charging ring 4 by the lower port of U-shaped thrust-augmenting nozzle 6 along the tangential direction of charging ring 4, the mixing solutions flowing into charging ring 4 cavity is after ring body cavity buffering, and from the inner side of charging ring 4, tapered opening 14 ejection enters hollow cylinder 7.The polymer molecule microscopic aggregates having trapped boron adsorbs at bubble surface, is taken away enter enlarging district 9 by rising bubble.In enlarging district 9, the foam produced collected by the froth paddle 10 driven by motor 11, and the boron in the foam of being discharged by foam outlet 12 is reclaimed in back extraction, discharges finally by salt lake brine outlet 3 salt lake brine having carried boron.
Specific embodiment 1
Get containing B
2o
3the salt lake brine 300ml of massfraction 0.1%, is filled to as shown in Figure 1 in air supporting column extractor.Blast air from gas feed 1 shown in figure, air-blowing speed is 0.1mL/min.Add polymer poly ethylene glycol PEG (molecular weight is for the 2000) aqueous solution 1.5mL of polymer quality mark 30% with the speed of 0.01mL/min from the aqueous solution of water-soluble polymers shown in Fig. 1 import 5.Collected the bubble foam on air supporting column extractor top by froth paddle 10, reclaim the boron in foam with hydrochloric acid back extraction, analyze the boron concentration in salt lake brine outlet 3 outflow salt lake brine water sample, calculating boron air supporting percentage extraction is 85%.
Specific embodiment 2
Get containing B
2o
3the salt lake brine 300ml of massfraction 3%, is filled to as shown in Figure 1 in air supporting column extractor.Blast nitrogen from gas feed 1 shown in figure, air-blowing speed is 100mL/min.Add polymkeric substance PEP-101 (EOPO) (molecular weight is for the 2500) aqueous solution 240mL of polymer quality mark 80% with the speed of 0.01mL/min from the aqueous solution of water-soluble polymers shown in Fig. 1 import 5.Collected the bubble foam on air supporting column extractor top by froth paddle 10, reclaim the boron in foam with hydrochloric acid back extraction, analyze the boron concentration in salt lake brine outlet 3 outflow salt lake brine water sample, calculating boron air supporting percentage extraction is 82%.
Specific embodiment 3
Get containing B
2o
3the salt lake brine 300ml of massfraction 0.01%, is filled to as shown in Figure 1 in air supporting column extractor.Blast air from gas feed 1 shown in figure, air-blowing speed is 20mL/min.Add the high molecular polymer polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer aqueous solution 30mL of high molecular polymer massfraction 8% with the speed of 2mL/min from the aqueous solution of water-soluble polymers shown in Fig. 1 import 5.Collected the bubble foam on air supporting column extractor top by froth paddle 10, reclaim the boron in foam with hydrochloric acid back extraction, analyze the boron concentration in salt lake brine outlet 3 outflow salt lake brine water sample, calculating boron air supporting percentage extraction is 80%.
Comparative example
Get containing B
2o
3massfraction is the pure boric acid aqueous solution 300ml of 0.01%, is filled in air supporting column extractor as shown in Figure 1.Blast air from gas feed 1 shown in figure, air-blowing speed is 20mL/min.Add the high molecular polymer polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer aqueous solution 60mL of high molecular polymer massfraction 8% with the speed of 2mL/min from the aqueous solution of water-soluble polymers shown in Fig. 1 import 5 under air-blowing state.Collect air-flotation column top liquid by froth paddle 10 scraping, analyze wherein boron concentration, and compared with exporting the 3 boron concentration flowed out in water sample with salt lake brine, result is consistent, illustrates that boron is not extracted.
Applicant states, the present invention illustrates method detailed of the present invention and device by above-described embodiment, but the present invention is not limited to above-mentioned method detailed and device, does not namely mean that the present invention must rely on above-mentioned method detailed and device could be implemented.Person of ordinary skill in the field should understand; any improvement in the present invention; to the equivalence replacement of raw material each in the inventive method and device and parts, ancillary component and the interpolation of accessory, concrete way choice etc., all drop within protection scope of the present invention and open scope.
Claims (22)
1. air supporting polymkeric substance is from a method for salt lake brine boron extraction, it is characterized in that, described method comprises the steps:
Salt lake brine containing boron is mixed with the water-soluble polymers aqueous solution in air supporting column extractor outer side wall U-shaped thrust-augmenting nozzle and contacts, Water-soluble Polymer Molecules salt condensation for removing water in salt lake brine is made to form polymer molecule microscopic aggregates, gained mixing solutions enters in air supporting column extractor through charging ring spray, the polymer molecule microscopic aggregates having trapped boron adsorbs at bubble surface, taken away by rising bubble, collect the foam produced in air supporting column extractor upper end, the boron in foam is reclaimed in back extraction.
2. the method for claim 1, is characterized in that, described method comprises the steps:
(1) Salt lake brine containing boron is filled in air supporting column extractor;
(2) pump into gas from air supporting column extractor lower end, adjustment pump airshed makes the gas pumped into be that air bubbles dispersion phase form is dispersed in salt lake brine;
(3) the water-soluble polymers aqueous solution is pumped into from air supporting column extractor outer side wall U-shaped thrust-augmenting nozzle, aqueous solutions of polymers at room temperature mixes with the salt lake brine of overflow and contacts in U-shaped thrust-augmenting nozzle, Water-soluble Polymer Molecules salt condensation for removing water in salt lake brine is made to form polymer molecule microscopic aggregates, gained mixing solutions enters in air supporting column extractor through charging ring spray, the polymer molecule microscopic aggregates having trapped boron adsorbs at bubble surface, is taken away by rising bubble;
(4) collect the foam produced in air supporting column extractor upper end, the boron in foam is reclaimed in back extraction.
3. method as claimed in claim 1 or 2, it is characterized in that, in described Salt lake brine containing boron, the concentration of boron is with B
2o
3meter, its mass percentage concentration is 0.01 ~ 3%.
4. method as claimed in claim 3, it is characterized in that, in described Salt lake brine containing boron, the concentration of boron is with B
2o
3meter, its mass percentage concentration is 0.3 ~ 3%.
5. method as claimed in claim 2, is characterized in that, step (2) described gas is selected from the combination of any one or at least two kinds in air, nitrogen or rare gas element.
6. method as claimed in claim 2, it is characterized in that, pumping into gas flow described in step (2) is 0.1 ~ 100mL/min.
7. method as claimed in claim 6, it is characterized in that, pumping into gas flow described in step (2) is 0.1 ~ 20mL/min.
8. method as claimed in claim 2, it is characterized in that, the speed that pumps into of the described water-soluble polymers aqueous solution of step (3) is 0.01 ~ 5mL/min.
9. method as claimed in claim 8, it is characterized in that, the speed that pumps into of the described water-soluble polymers aqueous solution of step (3) is 0.01 ~ 2mL/min.
10. the method as described in one of claim 1-2, it is characterized in that, described water-soluble polymers is polyoxyethylene glycol, polypropylene glycol, methoxy poly (ethylene glycol), methoxyl group polypropylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, PLURONIC F-127, polyox-yethylene-polyoxypropylene block copolymer, PEP-101, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, polypropylene glycol-polyoxyethylene glycol-mono—n—butylester triblock copolymer, the mixture of any one or at least two kinds in methylcellulose gum or Natvosol.
11. methods as claimed in claim 10, it is characterized in that, described water-soluble polymers is the mixture of any one or at least two kinds in PLURONIC F-127, polyox-yethylene-polyoxypropylene block copolymer, PEP-101, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer or polypropylene glycol-polyoxyethylene glycol-mono—n—butylester triblock copolymer.
12. methods as described in one of claim 1-2, it is characterized in that, be 100 listed as parts by weight with the water-soluble polymers aqueous solution, and the amount of water-soluble polymers is 8 ~ 80 weight parts.
13. methods as claimed in claim 12, it is characterized in that, be 100 listed as parts by weight with the water-soluble polymers aqueous solution, and the amount of water-soluble polymers is 30 ~ 80 weight parts.
14. methods as described in one of claim 1-2, it is characterized in that, be 100 parts by weight with Salt lake brine containing boron, and the add-on of the described water-soluble polymers aqueous solution is 0.5 ~ 80 weight part.
15. methods as claimed in claim 14, it is characterized in that, be 100 parts by weight with Salt lake brine containing boron, and the add-on of the described water-soluble polymers aqueous solution is 0.5 ~ 10 weight part.
16. methods as described in one of claim 1-2, is characterized in that, adopt to scrape bubble method and collect foam.
17. methods as described in one of claim 1-2, is characterized in that, do reverse-extraction agent back extraction reclaim boron in foam with hydrochloric acid.
18. 1 kinds of air supporting polymkeric substance, from the device of salt lake brine boron extraction, is characterized in that, described device is air supporting column extractor; Described air supporting column extractor comprises hollow cylinder, is provided with gas feed, is provided with gas distributor above gas feed bottom it; An annular, the tapered opening in inner side, the inner charging ring for cavity structure is provided with above gas distributor; Hollow cylinder outer side wall is provided with U-shaped thrust-augmenting nozzle, and its lower port is communicated with along the tangential direction of charging ring with charging ring; The hollow cylinder at the upper port place of U-shaped thrust-augmenting nozzle is provided with diversion trench; Described U-shaped thrust-augmenting nozzle is provided with the import of the water-soluble polymers aqueous solution, and the position of described water-soluble polymers aqueous solution import and the vertical range of charging ring are 1/20 ~ 1/10 of hollow cylinder height; The top of described hollow cylinder is provided with the enlarging district of top seal, and the sidewall in enlarging district is provided with foam outlet.
19. devices as claimed in claim 18, it is characterized in that, be provided with froth paddle in described enlarging district, it is with driven by motor.
20. devices as described in claim 18 or 19, it is characterized in that, described hollow cylinder upper end, near place of enlarging district, is provided with salt lake brine opening for feed, and hollow cylinder lower end is provided with salt lake brine outlet below charging ring, above gas distributor.
21. devices as described in claim 18 or 19, it is characterized in that, the height of described hollow cylinder is 2 ~ 10 meters, and aspect ratio is 10:1 ~ 100:1.
22. devices as claimed in claim 21, is characterized in that, the height of described hollow cylinder is 2 ~ 10 meters, and aspect ratio is 20:1 ~ 50:1.
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| CN107638960B (en) * | 2017-08-25 | 2019-11-22 | 中国科学院青海盐湖研究所 | The method of separating boron |
| CN107828961B (en) * | 2017-11-02 | 2024-04-05 | 中国科学院过程工程研究所 | Extraction method of rare earth element ions and obtained rare earth enrichment liquid |
| CN112451993B (en) * | 2020-11-25 | 2022-02-01 | 中国石油化工股份有限公司 | Spray extraction equipment and solvent extraction method |
| CN112657336B (en) * | 2020-12-03 | 2023-10-17 | 郑州大学 | Stable isotope floating extraction precise separation method |
| CN112538570B (en) * | 2020-12-03 | 2022-07-29 | 郑州大学 | Method for separating rare and noble metals based on floating extraction system |
| CN115611260B (en) * | 2022-12-15 | 2023-03-03 | 中国科学院过程工程研究所 | Method for extracting micro-bubble reinforced phosphate rock acidolysis solution |
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