CN106636688A - Extraction method for efficiently enriching and recovering low-concentration rare earth ions - Google Patents
Extraction method for efficiently enriching and recovering low-concentration rare earth ions Download PDFInfo
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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
- C22B59/00—Obtaining rare earth metals
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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
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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Abstract
The invention discloses an extraction method for efficiently enriching and recovering low-concentration rare earth ions. According to the extraction method, the enrichment of the low-concentration rare earth ions with an extreme ratio of more than 50 is completed by a gas-liquid-liquid three-phase system in a membrane dispersion micro-extractor, and the membrane dispersion micro-extractor is then used again for completing a reverse extraction process. The extraction method adopts the membrane dispersion micro-extractor to rapidly realize the extraction process of the rare earth ions with the extreme ratio on the basis that the gas-liquid-liquid three-phase system has the advantages of being high in mass transfer rate, short in mass transfer distance and large in specific surface area under the condition that the extreme ratio of water phase flow to oil phase flow is more than 50: 1, and the concentration of the rare earth ions in a water phase can reach the emission standard in China after extraction. Furthermore, the reverse extraction, which is from an organic phase to the water phase, of the rare earth ions is completed by using liquid-liquid extraction in the device, the concentration of the enriched rare earth ions is more than 20g/L after the reverse extraction is finished, and the organic phase can be recycled; therefore, the aim of enriching and recovering the rare earth ions is realized in a real sense.
Description
Technical field
The present invention relates to the solvent extraction and separation technical field of rare earth ion, specifically a kind of efficiently concentrating recovery low concentration
The extracting process of rare earth ion.
Background technology
Rare earth has the laudatory title of " industrial vitamin ", is important strategic resource.At present national economy has been widely used in
Every field, its application throughout the dozens of industry such as metallurgical industry, traditional agriculture, health care and high technology industry.So
And rare earth exploitation smelt and separation process in generate substantial amounts of low concentration (<100mg/L) rare earth ion raffinate or low dense
Degree rare earth ore leachate, if directly discharging, one is the pollution that can cause environment, and two is the significant wastage that can cause rare earth resources.It is dilute
Local products industry is the rare strong industry of China, and rare earth new material has become the indispensable material of China's items new and high technology, pin
To low concentration (<100ppm) for rare earth ion waste liquid, extraction process is selective strong, can pass through selection and the extraction work of extractant
The optimization of skill, reaches the effect of removal of impurities while rare earth is enriched with.But existing traditional solvent extraction technology and supporting with it
Industrial equipment is directed to the high concentration rare earth solution of g/L levels mostly, and is unsuitable for being enriched with from the water body of the very big scale of construction and carries
Take the object with separating-purifying low concentration, it is impossible to which the low concentration of rare earth ore leachate Extraction and enrichment for directly applying to mg/L levels is dilute
Soil.When processing low concentration of rare earth solution, in order to meet the pan feeding requirement of existing RE extraction separation process and later separation purification, enrichment
Pretreatment pressures are big.Therefore, to carry out rare earth element enriching and recovering using extraction, (aqueous phase stream amount is extremely compared：Oil phase stream
Amount>50:1) research under has important practical significance.
If wanting the enriching and recovering for realizing extremely comparing lower rare earth ion, need to overcome and compare brought mass transfer distance greatly
Greatly, the problems such as specific surface area is little, energy input is raised, extraction efficiency declines and is emulsified.Our (Chinese invention patents
CN201510467609.4) once hollow microlayer model structure is formed by introducing gas in microfluidic device low so as to realize reinforcing
The purpose of concentration rare earth ion extracting and enriching process.Liquid liquid system and gas-liquid-liquid system are studied.It is main to investigate
The time of staying, compare and the impact to extraction efficiency of gas phase flow rate these three factors.As a result show to introduce the extraction after gas
I.e. up to more than 90% in several seconds, its average external volume mass tranfer coefficient is 5-50 times when being not introduced into gas to rate.Work as initial concentration
For 30-90ppm when, its corresponding enrichment times is up to 200-450 times.Fast with reaction speed, the good advantage of concentration effect is
What additive method to be replaced.But the treating capacity of its rare earth feed liquid is 4mL/min, it is more difficult that equipment amplifies, and this is from real
The also very long segment distance of commercial Application.
The single channel invented before us and multi-channel membrane dispersion micro-extraction apparatus (Chinese invention patent ZL00105779.0,
ZL200510012114.9 it is) by the use of microporous barrier as mutually scattered medium, in film pressure at both sides difference more than the bar for penetrating pressure
Under part, one is mutually distributed in another phase and realizes that rapid mass transfer is separated.Because it has treating capacity big, dispersion yardstick is low, mass transfer
Area is big, and device is simple and the advantages of fast mass transfer rate, for solvent extraction process a kind of preferable equipment provided, is curing
Medicine, food and chemical field have a wide range of applications.What is more important, our (Chinese invention patents
CN201410583407.1 the stripping process of rare earth ion) was once studied in film disperses micro-extraction, was as a result shown dense in hydrochloric acid
Spend for 0.5mol/L, the time of staying, its stripping efficiency can be more than 90% less than under the conditions of 4s.
Therefore, the efficient air-liquid-liquid three phase extraction or reality under disperseing micro-extraction apparatus to be expected to both realize extremely comparing using film
Existing liquid liquid system stripping process, so as to lay a good foundation for the potential path of recovering rare earth ion set forth above.And the thinking
There is not yet document report.
The content of the invention
It is an object of the invention to provide a kind of mass transfer rate is fast, mass transfer is returned apart from the big efficiently concentrating of short, specific surface area
Receive low concentration of rare earth ion extracting process, to solve the problems, such as above-mentioned background technology in propose.
For achieving the above object, the present invention provides following technical scheme：
A kind of efficiently concentrating reclaims the extracting process of low concentration of rare earth ion, is completed in film dispersion micro-extraction apparatus
Then solution-air-liquid tri-phase system reuses film and disperses to the enrichment for extremely comparing lower low concentration of rare earth ion more than 50
Micro-extraction apparatus complete stripping process, for initial concentration for 5-200mg/L rare-earth ion solution, Jing extraction back extraction after rare earth from
Sub- concentration reaches 1-40g/L；Comprise the following steps that：
(1) configure low concentration of rare earth solion or mixed as water using factory's deionized water solution containing low concentration of rare earth
Liquid；Configuration organic phase solution, the wherein different monooctyl ester P507 of isooctyl phosphoric acid list is extractant, and kerosene is diluent；
(2) organic phase solution in nitrogen or compressed air and step (1) is respectively delivered to into one-level film dispersion micro-extraction
In device, the depressed structure of oil bag is formed；
(3) above-mentioned oil-gas mixture is flowed in secondary membrane dispersion micro-extraction apparatus, is cut by aqueous phase solution in step (1)
Cut, so as to form the hollow drop of oil-in-water bag gas；
(4) mixed phase containing dispersant liquid drop group is flowed in phase separation chamber through outlet, Jing split-phases, the water phase pole for obtaining
Low concentration of rare earth ion raffinate and organic phase, water phase extremely low concentration rare earth ion raffinate is directly discharged or as rare earth ion
Leachate recycle, organic phase be used for next step back extraction；
(5) during back extraction its continuous phase and dispersion phase be respectively organic phase and concentration in step (4) be 1.0-2.0mol/L
Hydrochloric acid solution be transported in film dispersion micro-extraction apparatus, through stopping and split-phase, i.e., concentration after be enriched with is 1-40g/L
The extractant of high concentration rare earth solion and unsupported rare earth ion.Organic extractant phase agent repetitive cycling is utilized, high-concentration dilute
Native solion is further isolated and purified using existing method；
As further scheme of the invention：The pH of aqueous phase solution is 3.00-5.00 in the step (1).
As further scheme of the invention：Selected rare-earth ion solution system should cover group of the lanthanides in the step (1)
Light middle heavy element in element, take respectively it is light in heavy element a kind of each or its mixture hydrochloric acid carry out dissolving prepared rare earth from
The sub- aqueous solution.
As further scheme of the invention：In the step (1) initial concentration of extractant be 1.0-2.0mol/L, water
Phase initial concentration solution<200mg/L.
As further scheme of the invention：The film for being adopted disperses micro-extraction apparatus for single channel and multichannel micro-extraction
Device, the gas flow in single channel micro-extraction apparatus be 10-100mL/min, organic phase flow be 0.1-2.0mL/min, aqueous phase stream
Measure as 10-100mL/min；In the range of 50-1000, treating capacity increases the port number of multichannel micro-extraction apparatus into corresponding multiple.
As further scheme of the invention：The flow-rate ratio of gas flow and organic phase flow is 50- in the step (2)
500：1, the flow-rate ratio of water phase and organic phase is 5-500 in the step (3)：1.
As further scheme of the invention：The size of disperse, hollow drop is 10-500 μm in the step (4).
Compared with prior art, the invention has the beneficial effects as follows：
The present invention is tied up to based on solution-air-liquid three-phase fine dispersion and extremely compared down with mass transfer rate soon, and mass transfer is apart from short
And the advantage that specific surface area is big, quickly realize extremely comparing lower low concentration of rare earth ion (5- using film dispersion micro-extraction apparatus
Extracting and enriching process 200mg/L), the water phase raffinate containing extremely low concentration rare earth ion can directly be discharged or made after the completion of extraction
Leachate for Rare Earth Mine is recycled.Meanwhile, using film dispersion micro-extraction apparatus rare earth ion is completed from having using liquid-liquid extraction
The back extraction of the opposite water phase of machine, the rare earth ion concentration that back extraction is enriched with after terminating can reach 1-40g/L, and organic phase is repeated and followed
Ring is utilized, and truly realizes the target of rare earth ion enriching and recovering.
Description of the drawings
Fig. 1 is method of the present invention schematic diagram.
Specific embodiment
The technical scheme of this patent is described in more detail with reference to specific embodiment.
Embodiment 1
Fig. 1 is referred to, with the aqueous hydrochloric acid solution of pH=4 the chloride of neodymium is dissolved, be made into rare-earth ion solution (initial concentration
For 90mg/L).Take homogeneous molten obtained by the different monooctyl ester of the isooctyl phosphoric acid list (P507) of 34mL and the sulfonated kerosene stirring mixing of 66mL
The concentration of liquid, wherein extractant is 1mol/L.Air valve, gas mass flow gauge, and the switch of two constant-flux pumps are opened, is passed through
The direction for adjusting five-way ball valve causes outlet pipe range to rest on 2m positions.Gas is dispersion in one-level film dispersion micro-extraction apparatus
Phase, organic phase is continuous phase；The depressed structure of oil bag is dispersion phase in secondary membrane dispersion micro-extraction apparatus, and continuous phase is that rare earth ion is molten
Liquid.Aqueous phase stream amount is adjusted to 40mL/min, and oil phase flow is 0.2mL/min, and gas phase flow rate is 90mL/min.Flow of fluid 5min
Afterwards, raffinate is connect to obtain from phase separation chamber water phase exit, its Concentration Testing adopts ICP-OES, within 2%, it extracts error range
Rate is taken up to more than 95%, raffinate Rare Earth Ion is 0.13mg/L.The extractant of supported rare earth ion is collected in oil phase outlet
Solution.Using the extraction agent solution of above-mentioned load as continuous phase, the hydrochloric acid of 1.0mol/L is dispersion phase.The two flow is respectively
8mL/min and 4mL/min, stopping after 5min can connect to obtain high concentration rare earth solion from phase separation chamber water phase outlet, quantitatively
Detected using ICP-OES after dilution, the rare earth ion after enrichment can arrive 18g/L.Oil phase exit connects to obtain unsupported rare earth
The extractant of ion, can be recycled.If operating condition need to be changed, the time of staying can be changed by adjusting outlet pipe range,
Adjustable three-phase flow.Operating condition repeats aforesaid operations after determining.
Embodiment 2
The chloride of europium is dissolved with the aqueous hydrochloric acid solution of pH=4, be made into rare-earth ion solution (initial concentration is 50mg/L).
The different monooctyl ester of the isooctyl phosphoric acid list (P507) of 34mL and the sulfonated kerosene stirring mixing gained uniform solution of 66mL are taken, wherein extracting
The concentration of agent is 1mol/L.Air valve, gas mass flow gauge, and the switch of two constant-flux pumps are opened, by adjusting five-way ball
The direction of valve causes outlet pipe range to rest on 2m positions.Gas is dispersion phase in one-level film dispersion micro-extraction apparatus, and organic phase is
Continuous phase；The depressed structure of oil bag is dispersion phase in secondary membrane dispersion micro-extraction apparatus, and continuous phase is rare-earth ion solution.Aqueous phase stream amount is adjusted
Save as 40mL/min, oil phase flow is 0.2mL/min, and gas phase flow rate is 90mL/min.After flow of fluid 5min, from phase separation chamber water
Phase exit connects to obtain raffinate, and its Concentration Testing adopts ICP-OES, error range within 2%, its extraction yield up to 95% with
On, raffinate Rare Earth Ion is 0.1mg/L.The extraction agent solution of supported rare earth ion is collected in oil phase outlet.By above-mentioned load
Extraction agent solution as continuous phase, the hydrochloric acid of 1.0mol/L is dispersion phase.The two flow is respectively 8mL/min and 4mL/min,
Stopping after 5min can connect to obtain high concentration rare earth solion from phase separation chamber water phase outlet, and after quantitative dilution ICP-OES is utilized
Detected, the rare earth ion after enrichment can arrive 10g/L.Oil phase exit connect unsupported rare earth ion extractant, can follow
Ring is used.If operating condition need to be changed, by adjusting outlet pipe range the time of staying can be changed, also can adjust three-phase flow.Behaviour
Make to repeat aforesaid operations after condition determines.
Embodiment 3
The chloride of erbium is dissolved with the aqueous hydrochloric acid solution of pH=4, be made into rare-earth ion solution (initial concentration is 10mg/L).
The different monooctyl ester of the isooctyl phosphoric acid list (P507) of 34mL and the sulfonated kerosene stirring mixing gained uniform solution of 66mL are taken, wherein extracting
The concentration of agent is 1mol/L.Air valve, gas mass flow gauge, and the switch of two constant-flux pumps are opened, by adjusting five-way ball
The direction of valve causes outlet pipe range to rest on 2m positions.Gas is dispersion phase in one-level film dispersion micro-extraction apparatus, and organic phase is
Continuous phase；The depressed structure of oil bag is dispersion phase in secondary membrane dispersion micro-extraction apparatus, and continuous phase is rare-earth ion solution.Aqueous phase stream amount is adjusted
Save as 40mL/min, oil phase flow is 0.2mL/min, and gas phase flow rate is 90mL/min.After flow of fluid 5min, from phase separation chamber water
Phase exit connects to obtain raffinate, and its Concentration Testing adopts ICP-OES, error range within 2%, its extraction yield up to 95% with
On, raffinate Rare Earth Ion is 0.05mg/L.The extraction agent solution of supported rare earth ion is collected in oil phase outlet.By above-mentioned load
Extraction agent solution as continuous phase, the hydrochloric acid of 1.0mol/L is dispersion phase.The two flow is respectively 8mL/min and 4mL/min,
Stopping after 5min can connect to obtain high concentration rare earth solion from phase separation chamber water phase outlet, and after quantitative dilution ICP-OES is utilized
Detected, the rare earth ion after enrichment can arrive 5g/L.Oil phase exit connect unsupported rare earth ion extractant, it is capable of circulation
Use.If operating condition need to be changed, by adjusting outlet pipe range the time of staying can be changed, also can adjust three-phase flow.Operation
Condition repeats aforesaid operations after determining.
Embodiment 4
The mixed chloride of praseodymium neodymium is dissolved with the aqueous hydrochloric acid solution of pH=4, (initial concentration is distinguished to be made into rare-earth ion solution
For 45mg/L).Take homogeneous molten obtained by the different monooctyl ester of the isooctyl phosphoric acid list (P507) of 34mL and the sulfonated kerosene stirring mixing of 66mL
The concentration of liquid, wherein extractant is 1mol/L.Air valve, gas mass flow gauge, and the switch of two constant-flux pumps are opened, is passed through
The direction for adjusting five-way ball valve causes outlet pipe range to rest on 2m positions.Gas is dispersion in one-level film dispersion micro-extraction apparatus
Phase, organic phase is continuous phase；The depressed structure of oil bag is dispersion phase in secondary membrane dispersion micro-extraction apparatus, and continuous phase is that rare earth ion is molten
Liquid.Aqueous phase stream amount is adjusted to 40mL/min, and oil phase flow is 0.2mL/min, and gas phase flow rate is 90mL/min.Flow of fluid 5min
Afterwards, raffinate is connect to obtain from phase separation chamber water phase exit, its Concentration Testing adopts ICP-OES, within 2%, it extracts error range
Rate is taken up to more than 95%, raffinate Rare Earth Ion is respectively 0.1mg/L and 0.06mg/L.Supported rare earth is collected in oil phase outlet
The extraction agent solution of ion.Using the extraction agent solution of above-mentioned load as continuous phase, the hydrochloric acid of 1.0mol/L is dispersion phase.The two
Flow is respectively 8mL/min and 4mL/min, and stopping after 5min can connect to obtain high concentration rare earth ion from phase separation chamber water phase outlet
Solution, is detected, the every kind of rare earth ion after enrichment can arrive 9g/L using ICP-OES after quantitative dilution.Oil phase exit connects
The extractant of unsupported rare earth ion is obtained, be can be recycled.If operating condition need to be changed, can be changed by adjusting outlet pipe range
The time of staying, also can adjust three-phase flow.Operating condition repeats aforesaid operations after determining.
Embodiment 5
The mixed chloride of samarium europium is dissolved with the aqueous hydrochloric acid solution of pH=4, (initial concentration is distinguished to be made into rare-earth ion solution
For 30mg/L).Take homogeneous molten obtained by the different monooctyl ester of the isooctyl phosphoric acid list (P507) of 34mL and the sulfonated kerosene stirring mixing of 66mL
The concentration of liquid, wherein extractant is 1mol/L.Air valve, gas mass flow gauge, and the switch of two constant-flux pumps are opened, is passed through
The direction for adjusting five-way ball valve causes outlet pipe range to rest on 2m positions.Gas is dispersion in one-level film dispersion micro-extraction apparatus
Phase, organic phase is continuous phase；The depressed structure of oil bag is dispersion phase in secondary membrane dispersion micro-extraction apparatus, and continuous phase is that rare earth ion is molten
Liquid.Aqueous phase stream amount is adjusted to 40mL/min, and oil phase flow is 0.2mL/min, and gas phase flow rate is 90mL/min.Flow of fluid 5min
Afterwards, raffinate is connect to obtain from phase separation chamber water phase exit, its Concentration Testing adopts ICP-OES, within 2%, it extracts error range
Rate is taken up to more than 95%, raffinate Rare Earth Ion is respectively 0.04mg/L and 0.06mg/L.It is dilute that load is collected in oil phase outlet
The extraction agent solution of native ion.Using the extraction agent solution of above-mentioned load as continuous phase, the hydrochloric acid of 1.0mol/L is dispersion phase.Two
Person's flow is respectively 8mL/min and 4mL/min, stop can connect from phase separation chamber water phase outlet after 5min high concentration rare earth from
Sub- solution, is detected, the every kind of rare earth ion after enrichment can arrive 6g/L using ICP-OES after quantitative dilution.Oil phase exit
Connect unsupported rare earth ion extractant, can be recycled.If operating condition need to be changed, can be changed by adjusting outlet pipe range
Become the time of staying, also can adjust three-phase flow.Operating condition repeats aforesaid operations after determining.
Embodiment 6
The mixed chloride of erbium thulium is dissolved with the aqueous hydrochloric acid solution of pH=4, (initial concentration is distinguished to be made into rare-earth ion solution
For 45mg/L).Take homogeneous molten obtained by the different monooctyl ester of the isooctyl phosphoric acid list (P507) of 34mL and the sulfonated kerosene stirring mixing of 66mL
The concentration of liquid, wherein extractant is 1mol/L.Air valve, gas mass flow gauge, and the switch of two constant-flux pumps are opened, is passed through
The direction for adjusting five-way ball valve causes outlet pipe range to rest on 2m positions.Gas is dispersion in one-level film dispersion micro-extraction apparatus
Phase, organic phase is continuous phase；The depressed structure of oil bag is dispersion phase in secondary membrane dispersion micro-extraction apparatus, and continuous phase is that rare earth ion is molten
Liquid.Aqueous phase stream amount is adjusted to 40mL/min, and oil phase flow is 0.2mL/min, and gas phase flow rate is 90mL/min.Flow of fluid 5min
Afterwards, raffinate is connect to obtain from phase separation chamber water phase exit, its Concentration Testing adopts ICP-OES, within 2%, it extracts error range
Rate is taken up to more than 95%, raffinate Rare Earth Ion is respectively 0.1mg/L and 0.16mg/L.Supported rare earth is collected in oil phase outlet
The extraction agent solution of ion.Using the extraction agent solution of above-mentioned load as continuous phase, the hydrochloric acid of 1.0mol/L is dispersion phase.The two
Flow is respectively 8mL/min and 4mL/min, and stopping after 5min can connect to obtain high concentration rare earth ion from phase separation chamber water phase outlet
Solution, is detected, the every kind of rare earth ion after enrichment can arrive 9g/L using ICP-OES after quantitative dilution.Oil phase exit connects
The extractant of unsupported rare earth ion is obtained, be can be recycled.If operating condition need to be changed, can be changed by adjusting outlet pipe range
The time of staying, also can adjust three-phase flow.Operating condition repeats aforesaid operations after determining.
Embodiment 7
The mixed chloride of cerium praseodymium neodymium is dissolved with the aqueous hydrochloric acid solution of pH=4, rare-earth ion solution (initial concentration point is made into
Wei 30mg/L).Take obtained by the different monooctyl ester of the isooctyl phosphoric acid list (P507) of 340mL and the sulfonated kerosene stirring mixing of 660mL
The concentration of one solution, wherein extractant is 1mol/L.Air valve, gas mass flow gauge, and the switch of two constant-flux pumps are opened,
Outlet pipe range is caused to rest on 2m positions by adjusting the direction of five-way ball valve.Gas is to divide in one-level film dispersion micro-extraction apparatus
Dephasing, organic phase is continuous phase；The depressed structure of oil bag is dispersion phase in secondary membrane dispersion micro-extraction apparatus, and continuous phase is that rare earth ion is molten
Liquid.Aqueous phase stream amount is adjusted to 400mL/min, and oil phase flow is 2mL/min, and gas phase flow rate is 900mL/min.Flow of fluid 5min
Afterwards, raffinate is connect to obtain from phase separation chamber water phase exit, its Concentration Testing adopts ICP-OES, within 2%, it extracts error range
Rate is taken up to more than 99%, total rare earth (TRE) ion concentration is less than 0.2mg/L in raffinate.Supported rare earth ion is collected in oil phase outlet
Extraction agent solution.Using the extraction agent solution of above-mentioned load as continuous phase, the hydrochloric acid of 1.0mol/L is dispersion phase.The two flow point
Not Wei 80mL/min and 40mL/min, stop 5min after can connect from phase separation chamber water phase outlet high concentration rare earth ion is molten
Liquid, is detected, the every kind of rare earth ion after enrichment can arrive 6g/L using ICP-OES after quantitative dilution.Oil phase exit connects
The extractant of unsupported rare earth ion, can be recycled.If operating condition need to be changed, can be changed by regulation outlet pipe range and be stopped
The time is stayed, three-phase flow is also can adjust.Operating condition repeats aforesaid operations after determining.
Embodiment 8
The mixed chloride of sm-eu-gd is dissolved with the aqueous hydrochloric acid solution of pH=4, rare-earth ion solution (initial concentration point is made into
Wei 30mg/L).Take homogeneous molten obtained by the different monooctyl ester of the isooctyl phosphoric acid list (P507) of 34L and the sulfonated kerosene stirring mixing of 66L
The concentration of liquid, wherein extractant is 1mol/L.Open air valve, gas mass flow gauge, and the switch of two constant-flux pumps, one-level
Gas is dispersion phase in film dispersion micro-extraction apparatus, and organic phase is continuous phase；The depressed structure of oil bag is in secondary membrane dispersion micro-extraction apparatus
Dispersion phase, continuous phase is rare-earth ion solution.Aqueous phase stream amount is adjusted to 4L/min, and oil phase flow is 200mL/min, gas phase flow rate
For 9L/min.After flow of fluid 1min, raffinate is connect to obtain from phase separation chamber water phase exit, its Concentration Testing adopts ICP-OES, by mistake
Within 2%, up to more than 99%, total rare earth (TRE) ion concentration is 0.16mg/L to its extraction yield to difference scope in raffinate.Oil phase goes out
Mouth collects the extraction agent solution of supported rare earth ion.Using the extraction agent solution of above-mentioned load as continuous phase, the salt of 1.0mol/L
Acid is dispersion phase.The two flow is respectively 8L/min and 4L/min, and stopping can connect after 2min from phase separation chamber water phase outlet
High concentration rare earth solion, is detected, the rare earth ion after enrichment can arrive 6g/L using ICP-OES after quantitative dilution.Oil
Phase exit connect unsupported rare earth ion extractant, can be recycled.If operating condition need to be changed, by adjusting outlet
Pipe range can change the time of staying, also can adjust three-phase flow.Operating condition repeats aforesaid operations after determining.
Embodiment 9
The mixed chloride of erbium thulium ytterbium is dissolved with the aqueous hydrochloric acid solution of pH=4, rare-earth ion solution (initial concentration point is made into
Wei 30mg/L).Take homogeneous obtained by the different monooctyl ester of the isooctyl phosphoric acid list (P507) of 34mL and the sulfonated kerosene stirring mixing of 66mL
The concentration of solution, wherein extractant is 1mol/L.Air valve, gas mass flow gauge, and the switch of two constant-flux pumps are opened, is led to
The direction of five-way ball valve is overregulated so that outlet pipe range rests on 2m positions.Gas is dispersion in one-level film dispersion micro-extraction apparatus
Phase, organic phase is continuous phase；The depressed structure of oil bag is dispersion phase in secondary membrane dispersion micro-extraction apparatus, and continuous phase is that rare earth ion is molten
Liquid.Aqueous phase stream amount is adjusted to 40mL/min, and oil phase flow is 0.2mL/min, and gas phase flow rate is 90mL/min.Flow of fluid 5min
Afterwards, raffinate is connect to obtain from phase separation chamber water phase exit, its Concentration Testing adopts ICP-OES, within 2%, it extracts error range
Rate is taken up to more than 95%, total rare earth (TRE) ion concentration is 0.25mg/L in raffinate.Supported rare earth ion is collected in oil phase outlet
Extraction agent solution.Using the extraction agent solution of above-mentioned load as continuous phase, the hydrochloric acid of 1.0mol/L is dispersion phase.The two flow point
Not Wei 8mL/min and 4mL/min, stop 5min after can connect to obtain high concentration rare earth solion from phase separation chamber water phase outlet,
Detected using ICP-OES after quantitative dilution, the rare earth ion after enrichment can arrive 6mg/L.Oil phase exit connects unsupported
The extractant of rare earth ion, can be recycled.If operating condition need to be changed, when can change stop by adjusting outlet pipe range
Between, also can adjust three-phase flow.Operating condition repeats aforesaid operations after determining.
Leaching ore deposit tail washings rare earth ion water solution system (total concentration 200mg/L) proposed for certain enterprise is tested,
Extraction and stripping process are operated continuously.The sulfonated kerosene of the different monooctyl ester of the isooctyl phosphoric acid list (P507) and 660mL that take 340mL is stirred
Mixing gained uniform solution is mixed, the wherein concentration of extractant is 2mol/L.Opening air valve, gas mass flow gauge, and two
The switch of constant-flux pump.Gas is dispersion phase in one-level film dispersion micro-extraction apparatus, and organic phase is continuous phase；Secondary membrane disperses micro-extraction
The depressed structure of oil bag is dispersion phase in device, and continuous phase is rare-earth ion solution.Aqueous phase stream amount is adjusted to 400mL/min, oil phase flow
For 4mL/min, gas phase flow rate is 900mL/min.After flow of fluid 5min, raffinate is connect to obtain from phase separation chamber water phase exit, its
Concentration Testing adopts ICP-OES, error range within 2%, its extraction yield up to more than 99%, total rare earth (TRE) ion in raffinate
Concentration is 0.20mg/L.The extraction agent solution of supported rare earth ion is collected in oil phase outlet.The extraction agent solution of above-mentioned load is made
For continuous phase, the hydrochloric acid of 2.0mol/L is dispersion phase.The two flow is respectively 80mL/min and 40mL/min, and stopping can after 5min
High concentration rare earth solion is connect to obtain from phase separation chamber water phase outlet, is detected using ICP-OES after quantitative dilution, be enriched with
Total rare earth (TRE) ion concentration afterwards can arrive 20g/L.Oil phase exit connect unsupported rare earth ion extractant, can be recycled.
If operating condition need to be changed, by adjusting outlet pipe range the time of staying can be changed, also can adjust three-phase flow.Operating condition is true
Repeat aforesaid operations after fixed.
The film dispersion micro-extraction apparatus of the present invention are used for the extracting process of low concentration of rare earth ion in enriching and recovering industrial wastewater
Simple to operate, treasury is negated and extracted in one, the quick target for realizing enrichment rare earth ion.For extremely comparing, lower extraction is difficult to ask
Topic, is addressed using the method for introducing gas diminution mass transfer distance increase specific surface area.Stripping process is existed using liquid-liquid extraction
Routine is compared lower operation and is capable of achieving.High concentration rare earth ion concentration Jing after processing is more than 20g/L, extremely low dilute in raffinate
Native ion concentration can reach discharging standards.Its energy consumption is little, and mass transfer is fast, is advantageously implemented the industry that rare earth resources are recycled
Change, be that the proposition in above-mentioned path is laid a good foundation.
Single channel for the being enriched with rare earth ion and multi-channel membrane dispersion micro-extraction apparatus of the present invention, the hole of its miillpore filter
1-100 μm of footpath, drop size is in 2-500 μ ms after dispersion, and the gained droplet distribution under conditions of operating parameter determines
Good, the size uniformity of property.Compared with the legacy equipments such as mixer-settler, its drop size is substantially reduced, and mass transfer specific surface area increases.
Simultaneously the microstructural extractor can carry out reliable amplification, and to the treating capacity of rare-earth ion solution 10mL/min-10m is can reach3/ h,
Potential commercial Application for the technology provides equipment guarantee.
The extracting process for reclaiming enriching low-concentration rare earth ion of the present invention, the extraction in the case where extremely comparing is adopted
Solution-air-liquid three phase extraction system, with traditional liquid-liquid diphase extraction phase ratio, the structure of this hollow drop largely increases
Mass transfer area, improves mass-transfer efficiency, while the introducing of gas causes the density of the depressed structure of oil bag to have compared with simple oil droplet
Reduced, be more beneficial for the floating of oil droplet, be difficult emulsification.
The better embodiment of this patent is explained in detail above, but this patent is not limited to above-mentioned embodiment party
Formula, in the ken that one skilled in the relevant art possesses, can be with the premise of without departing from this patent objective
Various changes can be made.
Claims (7)
1. a kind of efficiently concentrating reclaims the extracting process of low concentration of rare earth ion, it is characterised in that be to disperse micro-extraction apparatus in film
In complete solution-air-liquid tri-phase system to the enrichment for extremely comparing lower low concentration of rare earth ion more than 50, it is then sharp again
Stripping process is completed with film dispersion micro-extraction apparatus, for initial concentration is the rare-earth ion solution of 5-200mg/L, Jing extracts back extraction
Afterwards rare earth ion concentration reaches 1-40g/L；Comprise the following steps that：
(1) low concentration of rare earth solion is configured or using factory's deionized water solution containing low concentration of rare earth as aqueous phase solution；Match somebody with somebody
Organic phase solution is put, the wherein different monooctyl ester P507 of isooctyl phosphoric acid list is extractant, and kerosene is diluent；
(2) organic phase solution in nitrogen or compressed air and step (1) is respectively delivered in one-level film dispersion micro-extraction apparatus,
Form the depressed structure of oil bag；
(3) above-mentioned oil-gas mixture is flowed in secondary membrane dispersion micro-extraction apparatus, by the shearing of aqueous phase solution in step (1),
So as to form the hollow drop of oil-in-water bag gas；
(4) mixed phase containing dispersant liquid drop group is flowed in phase separation chamber through outlet, and Jing split-phases, the water for obtaining is mutually extremely low dense
Degree rare earth ion raffinate and organic phase, water phase extremely low concentration rare earth ion raffinate is directly discharged or as the leaching of rare earth ion
Go out liquid recycling, organic phase is used for next step back extraction；
(5) during back extraction its continuous phase and dispersion phase be respectively organic phase and concentration in step (4) for 1.0-2.0mol/L salt
Acid solution is transported in film dispersion micro-extraction apparatus, and through stop and split-phase, that is, the concentration after being enriched with is highly concentrated for 1-40g/L's
The extractant of degree rare-earth ion solution and unsupported rare earth ion.Organic extractant phase agent repetitive cycling utilize, high concentration rare earth from
Sub- solution is further isolated and purified using existing method.
2. efficiently concentrating according to claim 1 reclaims the extracting process of low concentration of rare earth ion, it is characterised in that described
The pH of aqueous phase solution is 3.00-5.00 in step (1).
3. efficiently concentrating according to claim 1 reclaims the extracting process of low concentration of rare earth ion, it is characterised in that described
Selected rare-earth ion solution system should cover the light middle heavy element in lanthanide series in step (1), and light middle heavy element is taken respectively
In each a kind of or its mixture hydrochloric acid carry out dissolving the prepared rare earth ion aqueous solution.
4. the extracting process of low concentration of rare earth ion is reclaimed according to the arbitrary described efficiently concentrating of claim 1-3, and its feature exists
In, in the step (1) initial concentration of extractant be 1.0-2.0mol/L, aqueous phase solution initial concentration<200mg/L.
5. efficiently concentrating according to claim 4 reclaims the extracting process of low concentration of rare earth ion, it is characterised in that adopted
Film dispersion micro-extraction apparatus are single channel and multichannel micro-extraction apparatus, and the gas flow in single channel micro-extraction apparatus is 10-
100mL/min, organic phase flow is 0.1-2.0mL/min, and aqueous phase stream amount is 10-100mL/min；Multichannel micro-extraction apparatus it is logical
In the range of 5-1000, treating capacity increases road number into corresponding multiple.
6. efficiently concentrating according to claim 4 reclaims the extracting process of low concentration of rare earth ion, it is characterised in that described
The flow-rate ratio of gas flow and organic phase flow is 50-500 in step (2)：1, the stream of water phase and organic phase in the step (3)
Amount is than being 50-500：1.
7. efficiently concentrating according to claim 4 reclaims the extracting process of low concentration of rare earth ion, it is characterised in that described
The size of disperse, hollow drop is 10-500 μm in step (4).
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