CN102284190A - Three-phase solvent air-assist continuous extraction method - Google Patents
Three-phase solvent air-assist continuous extraction method Download PDFInfo
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Abstract
The invention relates to a three-phase solvent air-assist continuous extraction method. The method is performed by using three-phase solvent air-assist continuous extraction equipment. The equipment comprises an air flotation column with a gas inlet at the bottom, wherein the air flotation column comprises a bottom-phase mass transfer region, an intermediate-phase mass transfer region and a top-phase mass transfer region from bottom to top in sequence; a salt water phase containing an organic matter or a ionic substance to be separated is filled in the bottom-phase mass transfer region; a polymer phase is filled in the intermediate-phase mass transfer region; an organic solvent phase is filled in the top-phase mass transfer region; the bottom-phase mass transfer region also comprises a gas distributor which is positioned at the bottom of the bottom-phase mass transfer region; a partition plate with holes is also arranged between the bottom-phase mass transfer region and the intermediate-phase mass transfer region; gas is introduced into the air flotation column from the gas inlet; produced bubbles carry with the organic matter or the ionic substance to be separated in the salt water phase to transfer upwards; and the organic matter or the ionic substance in a lower salt water phase is extracted into the polymer phase filled in the intermediate-phase mass transfer region and the organic solvent phase filled in the top-phase mass transfer region to finish a three-phase solvent air-assist continuous extraction process.
Description
Technical field
The present invention relates to a kind of three phase solvent gas and help continuous extration method.
Technical background
Along with development of modern industry, people have proposed more and more higher requirement to isolation technics.The strictness of the degree of depth utilization of the preparation of high purity material, resource, the deep processing of product, environmental improvement standard implements to have promoted the fast development of separation science.High-level requirement is embodied in that separation system becomes increasingly complex, constituent content to be separated is more and more littler, character separate object is more and more close to modern industry to isolation technics, impels the appearance of some new separation technologies thus.Solvent extraction technology has wide application background as a kind of traditional separation process in the separation science field.In recent years, some emerging extraction and separation technologies such as cloud point extraction, micelle reverse micelle extraction, aqueous two-phase extraction, liquid-liquid-liquid three phase extraction, air assisted solvent extraction technology etc. are constantly further developed and are used.
In the middle of these novel extraction technology, liquid-liquid-liquid three phase extraction technology is obtaining fast-developing in recent years and is using the advantage that the good adaptability of complex system, good separating effect separated with one step of multiple target component with it.Disclose a kind of three-phase system that constitutes by butyl acetate-polyethylene glycol-ammonium sulfate-water as CN1324795 and be used to handle the technology of penicillin fermentation filtrate, has remarkable advantages than traditional two-phase extraction, researcher afterwards is applied to the three phase extraction technology fields such as extraction of multicomponent wastewater treatment, natural drug active ingredient again, has embodied many advantages of three phase extraction technology.Aspect the development of liquid-liquid-liquid three phase extraction equipment, liquid-liquid-liquid three phase continuous extraction vibrating sieve plate tower (CN1442223), liquid-liquid-liquid triphase horizontal continuous lifting stirring extraction device relevant extraction equipments such as (CN1463782) develop in succession, for the industrialization of liquid-liquid-liquid three phase extraction provides the reliable device support.Yet the liquid-liquid-liquid three phase extraction equipment of traditional complete mixed type relates to organic solvent in the solution loss of salt water, and the secondary pollution problem of salt water and organic solvent.Therefore, adopt new mass transfer pattern, the mode of operation of abandoning the complete mixed type of three-phase has important facilitation to improving liquid-liquid-liquid three phase extraction technology.
Summary of the invention
The object of the present invention is to provide a kind of three phase solvent gas to help continuous extration method, mass transfer rate when adopting this gas to help continuous extration method can accelerate the three-phase solvent extraction, avoided the organic solvent on the upper strata in three phase solvents to contact with the direct of salt water of lower floor, reduced the solution loss of the organic solvent on the polymer phase in intermediate layer and upper strata, and can reduce the loss of extractant (polymer phase in intermediate layer with the organic solvent on upper strata mutually) and the secondary pollution of raffinate phase (the salt water of lower floor) at the salt aqueous phase of lower floor.
Three phase solvent gas of the present invention help continuous extration method to carry out using a kind of three phase solvent gas to help on the continuous extraction equipment, wherein, described equipment comprises that the bottom has the air-flotation column of gas access, described air-flotation column comprises following phase mass-transfer zone, middle phase mass-transfer zone from the bottom to top successively and goes up mass-transfer zone mutually, wherein, be filled with the salt water in the phase mass-transfer zone under described, described salt aqueous phase contains organic matter to be separated or ionic species; Described down phase mass-transfer zone comprises the gas distributor that is positioned at phase mass-transfer zone bottom down, be positioned at phase mass-transfer zone top down the import of salt water, be positioned at the salt water outlet of phase mass-transfer zone bottom down; Be filled with polymer phase in the phase mass-transfer zone in described; The phase mass-transfer zone comprises that the polymer phase of mass-transfer zone bottom exports with being arranged in mutually in the polymer phase import that is arranged in phase mass-transfer zone top in described; Described going up in the phase mass-transfer zone is filled with the organic solvent phase; The described phase mass-transfer zone of going up comprises that the organic solvent of mass-transfer zone bottom exports mutually with being positioned at mutually in the organic solvent phase import that is positioned at phase mass-transfer zone top; Between described phase mass-transfer zone down and the middle phase mass-transfer zone dividing plate that has the hole is installed also;
The described gas access of gas from described air-flotation column bottom fed the air-flotation column, the gas that feeds enters described lower floor salt aqueous phase after by described gas distributor and carries out bubbling, the bubble that produces is carrying the organic matter described to be separated or the ionic species of described salt aqueous phase and is upwards transmitting, the organic matter to be separated of lower floor's salt aqueous phase or ionic species are through phase mass-transfer zone in described and the described mass-transfer zone mutually of going up, in the polymer phase of filling in the phase mass-transfer zone during the organic matter of lower floor's salt aqueous phase or ionic species are extracted to last mass-transfer zone mutually in the organic solvent of filling mutually in, finish three phase solvent gas and help the continuous extraction process.
According to the present invention, described salt water and polymer phase can be filled in described corresponding described following mass-transfer zone mutually, middle phase mass-transfer zone mutually in every way with organic solvent and go up in the phase mass-transfer zone.Generally, help in the continuous extraction process at three phase solvent gas, with in the described down phase mass-transfer zone not cracked ends salt solution export the identical flow of the salt water after the raffinate of outflow mutually, constantly in described phase mass-transfer zone down, replenish the new salt water that contains organic matter to be separated or ionic species by the import of salt water; With the identical flow of the polymer phase after the raffinate that flows out of cracked ends polymer phase outlet not in the phase mass-transfer zone in described, by the continuous additional new polymer phase in the phase mass-transfer zone to described in of polymer phase import; With the described identical flow of going up in the phase mass-transfer zone organic solvent phase after the raffinate that cracked ends organic solvent not exports outflow mutually, constantly replenish new organic solvent phase in the phase mass-transfer zone to described going up by the import of organic solvent phase.
The volume of described down phase mass-transfer zone account for air-flotation column cumulative volume 60～80%, be preferably 75～80%; In the volume of phase mass-transfer zone account for air-flotation column cumulative volume 10～20%, be preferably 10～15%; The volume of last phase mass-transfer zone account for air-flotation column cumulative volume 10～20%, be preferably 10～15%.
The present invention is not particularly limited the speed of the gas that fed,, can also can be high gas speed for low gas velocity that is, for example, the speed of the gas of feeding can for greater than 0ml/min smaller or equal to 80ml/min; In order to realize the raising of mass transfer velocity, preferably under high gas speed, carry out, that is, the speed of the gas of feeding is 40～80ml/min.Described gas can be selected from any not with salt water, polymer phase and organic solvent mutually in any gas of substance reaction, under the preferable case, described gas be selected from inert gas (as nitrogen, argon gas) or airborne one or more.
The salt water of filling in the described down phase mass-transfer zone and down mutually in the mass-transfer zone additional new salt water form by water and inorganic salts, wherein the mass percentage concentration scope of the inorganic salts of salt aqueous phase is 20～40%.
According to the present invention,, therefore, can select to satisfy the salt of its requirement according to the kind of material to be separated because different materials to be separated has different hydrophobicity (different solubility).The inorganic salts of described salt aqueous phase are selected from one or more in sulfate, phosphate, the carbonate.
The new organic matter to be separated that organic matter to be separated that the salt aqueous phase of filling in the described phase mass-transfer zone down contains and the salt aqueous phase that replenishes contain is a hydrophobic organic compound; The new ionic species to be separated that ionic species to be separated that the salt aqueous phase of filling in the described phase mass-transfer zone down contains and the salt aqueous phase that replenishes contain is inorganic metal ion or nonmetallic ion.When being ionogenic organic monoacid or weak base according to the contained organic matter of salt water, (determine by pKa or pKb value according to soda acid to respective value for the pH value of available inorganic acid and/or inorganic base adjusting salt water, the general pH value is 2～11), be beneficial to control being separated from each other between weak acid and/or the weak base.
Described hydrophobic organic compound can be selected from one or more in phenol, halogenated hydrocarbons, halogenated aryl hydrocarbon of pigment, phenol, replacement etc.Described inorganic metal ion can be selected from one or more in the metal ions such as Fe, Cu, Ir, Rh, Cr, U, Co, Cd, Pd, Pt; Described nonmetallic ion is nonmetallic ions such as I, As or their mixture etc.
The phenol of described replacement is nitrophenol, chlorophenol or their mixture etc.
Described halogenated hydrocarbons is the halogenated aliphatic hydrocarbon of C6～C12, and halogen is F, Cl or Br.
Described halogenated aryl hydrocarbon is halogeno-benzene or halogenated biphenyl, and halogen is F, Cl or Br.
The new polymer phase that replenishes in the polymer phase of filling in the phase mass-transfer zone in described and the middle mass-transfer zone mutually is the aqueous solution of polymer, and wherein the mass percentage concentration of the polymer in the polymer phase is 40～60%.
Polymer in the described polymer phase is selected from one or more in polyethylene glycol (PEG), polyethylene glycol-propane diols statistic copolymer (EOPO), the polyethylene glycol-propane diols-polyethylene glycol three close block copolymers (PEO-PPO-PEO).
Described go up the organic solvent of filling in the phase mass-transfer zone mutually and in the last mass-transfer zone mutually additional new organic solvent be organic solvent mutually, described organic solvent is selected from C
6～C
12Alkane, aromatic hydrocarbons, alkane substitute, alcohols, ketone, ethers, ester class, phosphine class, amine in one or more.
Described aromatic hydrocarbons is a kind of in benzene,toluene,xylene, the ethylo benzene.
Described alkane substitute is C
6～C
12A kind of in the halogenated alkane (halogen is F, Cl or Br).
Described alcohols is a kind of in octanol, the diethylhexyl alcohol.
Described ketone is a kind of in methyl iso-butyl ketone (MIBK), 2-heptanone, the cyclohexanone.
Described ethers is a kind of in propyl ether, isopropyl ether, the butyl ether.
Described ester class is a kind of in butyl acetate, amyl acetate, the methyl benzoate.
Described phosphine class is a kind of in tributyl phosphate, di(2-ethylhexyl)phosphate (2-ethylhexyl) ester, 2-ethylhexyl phosphoric acid list (2-ethylhexyl) ester.
Described amine is a kind of in trioctylamine, trialkylamine, the chlorination trialkyl methylamine.
The described dividing plate that has the hole can be the various dividing plates that have the hole, and under the preferable case, the described dividing plate that has the hole is the various oscillating screen plates of distribution grid with holes or this area routine; The described dividing plate that has the hole is distribution grid with holes or oscillating screen plate; The pore size in the hole on described distribution grid with holes or the oscillating screen plate can be 1～3mm, and percent opening is 20～50% (hole area accounts for the percentage of plate surface area).For example, the diameter in hole is 2mm, and percent opening is 27% a stainless steel sieve plate etc.
When the described dividing plate that has the hole is distribution grid with holes, can also further be equipped with filler on the described distribution grid with holes, the filler of described laying accounts for 2～5% of middle phase mass-transfer zone volume.The filler of laying further reaches and prevents the purpose of polymer phase to salt water back-mixing.Described filler can be bead or quartz spring shape filler etc.
Described gas distributor is the sand core funnel of using always, and preferred aperture is 4～70 microns a sand core funnel.As this area model commonly used is that the aperture of G1 series is 50～70 microns a sand core funnel, model is that the aperture of G2 series is 30～50 microns a sand core funnel, model is that the aperture of G3 series is 16～30 microns a sand core funnel, and model is that the aperture of G4 series is 4～7 microns a sand core funnel.
Described three phase solvent gas help the used extraction equipment of continuous extration method can also comprise auxiliary equipment, for example spinner flowmeter, surge tank and gas cylinder; Wherein, described gas cylinder is connected with the air inlet of described surge tank by pipeline, and the gas vent of surge tank is connected by the described gas access of pipeline with described air-flotation column bottom, and gas is provided in air-flotation column; On the gas vent of described surge tank and pipeline that the described gas access of described air-flotation column bottom is connected, described spinner flowmeter is installed, can further on this pipeline, installs valve additional simultaneously, and can control gas flow by spinner flowmeter.
For the ease of real-time sample analysis, further be provided with first thief hole on the air-flotation column of phase mass-transfer zone on described; In described, further be provided with second thief hole on the air-flotation column of phase mass-transfer zone; On the air-flotation column of described phase mass-transfer zone down, further be provided with the 3rd thief hole, the 4th thief hole, the 5th thief hole, the 6th thief hole from top to bottom.
Under the preferable case, the top of phase mass-transfer zone can also be provided with the expansion phase-separating section on described air-flotation column, so that charging and carry out gas-liquid separation; Described expansion phase-separating section is the container of back taper, and the end opening of conical vessel and described air-flotation column join, and the diameter suitable for reading of conical vessel is greater than the diameter of described air-flotation column.
A kind of three phase solvent gas of use of the present invention help continuous extraction equipment to carry out three phase solvent gas when helping continuous extraction, and its method of operating can also can be continued operation for intermittently operated (closing the terminal valve of each phase this moment).
The objective of the invention is to realize by the following technical solutions:
Gas in the gas cylinder is by spinner flowmeter control gas speed, gas is when the gas distributor bottom phase mass-transfer zone under the air-flotation column, be broken up into many micro-bubbles, these micro-bubbles at the salt aqueous phase limit rising edge that is rich in solute (organic matter to be separated or ionic species) by in the absorption of bubble surface, the gas that air bubble liquid-membrane is carried secretly and is entrained in the bubble is medium, organic matter to be separated in the saline solution or ionic species are delivered to polymer phase and salt aqueous phase interface, bubble partial crushing by boundary the time is sent to polymer phase to the solute of carrying secretly (organic matter to be separated or ionic species), simultaneously since the solute (organic matter to be separated or ionic species) that the effect polymer phase of bubble and salt aqueous phase interface are brought in constant renewal in also the mode by molecular diffusion enter polymer phase, so just finished solute (organic matter to be separated or ionic species) from the salt solution mass transfer of polymer phase in opposite directions.
Meanwhile, micro-bubble is when rising to the polymer phase interface, because distribution grid with holes and on the obstruct of filler, the part micro-bubble this coalescence become air pocket and pass distribution grid with holes and on filler, rise to the polymer body phase along the space between the filler, in the process that bubble rises, because the surface action of filler, make to rise to the bubble further coalescence of polymer body in mutually along the space between the filler and become air pocket; Or micro-bubble is when rising to the polymer phase interface, because the obstruct of oscillating screen plate, the part micro-bubble becomes air pocket and passes oscillating screen plate to rise to the polymer body phase at this coalescence, in the process that bubble rises, because the surface action of oscillating screen plate, make to rise to the bubble further coalescence of polymer body in mutually and become air pocket; Like this because distribution grid with holes and on filler or owing to the iris action of oscillating screen plate has stoped the salt water owing to the volumetric expansion that bubble causes enters polymer phase, polymer phase because distribution grid with holes and on filler or because the fierce back-mixing with the salt water has been avoided under high gas speed in the obstruct of oscillating screen plate, thereby realized the three phase extraction stable operation under high gas speed, reduced back-mixing to greatest extent.
Bubble in polymer phase is by the absorption at bubble surface, the medium effect of gas that air bubble liquid-membrane is carried secretly and is entrained in the bubble is delivered to upper strata organic solvent phase to part solute (organic matter to be separated or ionic species), upper strata organic solvent phase selectivity extracts one or more components, meanwhile, because solute (organic matter to be separated or ionic species) is brought in constant renewal at organic solvent boundary and polymer phase interface under the effect of bubble, part solute (organic matter to be separated or ionic species) enters the organic solvent phase by the molecular diffusion effect, has so just finished solute (organic matter to be separated or ionic species) from the transmittance process of polymer phase to the organic solvent phase.
In the mass transport process between polymer phase and organic solvent phase, because middle phase mass-transfer zone has the effect of the dividing plate in hole, most of micro-bubble coalescence is an air pocket, by the polymer phase body time, can cross so smoothly by and can not take place because the less polymer phase density that causes of micro-bubble buoyancy diminishes, thereby cause polymer phase to make progress floating and, kept the stability of liquid-liquid-liquid three phase extraction system effectively in the situation that organic solvent stops on mutually.
In whole mass transport process, be not only applicable to the three-phase mass transfer under the low gas velocity, be particularly useful for three-phase mass transport process under the high gas speed.The intermittently operated process not only can be adapted to, and the continuous extraction process can be realized.
Gas under the high gas speed of three phase solvents of the present invention helps continuous extraction process, is particularly useful for the weak solution multicomponent system, compares with the salt water by reduction organic solvent phase, polymer phase like this, can access higher accumulation rate, and the treating capacity of salt water is big.Polymer phase is easy to back extraction mutually with organic solvent and recycles.
Air assisted solvent extraction of the prior art is to utilize organic matter to be separated and/or ionic species to carry and be entrained in the medium effect of gas in the bubble secretly at absorption, the air bubble liquid-membrane of bubble surface, the organic matter to be separated in the salt water water and/or ionic species be sent to organic solvent mutually in, thereby realize the organic matter to be separated and/or the concentration and separation of ionic species.The advantage of air assisted solvent extraction is to have higher bioaccumulation efficiency for the volatility organic matter to be separated and/or the weak solution of ionic species, and owing to be unidirectional mass transfer under the bubble booster action, organic solvent has been avoided and the mixing fully of main body water mutually, has reduced the solution loss of organic solvent and to the secondary pollution of water.
The present inventor has proposed gas and has helped the three-phase solvent extraction technology by liquid-liquid-liquid three phase extraction technology and air assisted solvent extraction technology are combined.Method of the present invention also can adopt the mode of intermittently operated, under the situation that salt solution, aqueous solutions of polymers, this three-phase height of organic solvent are compared, still can obtain mass transfer effect preferably, with o-nitrophenol and p-nitrophenol serves as in the waste water system of simulation solute, in 30 minutes, the clearance of o-nitrophenol and p-nitrophenol reaches 82% and 81% (experiment value) respectively.The more important thing is,, especially go up the transfer rate of solute between phase mass-transfer zone and the middle phase mass-transfer zone in order to obtain mass transfer rate faster, just need be in (for example 40～80ml/min) times operations of high gas speed.The present inventor is provided with the dividing plate in hole cleverly between the salt water of air-flotation column and polymer phase, and preferably on described distribution grid with holes, lay filler, because the effect of distribution grid with holes and filler or oscillating screen plate, can reduce the back-mixing of polymer phase greatly to the salt aqueous phase, thereby be specially adapted under high gas speed, operate, and improved mass transfer velocity greatly, guaranteed simultaneously to help the stability of three-phase solvent-extraction system and the serialization that gas helps three phase extraction, helped the application of three-phase solvent extraction in practical systems to have great importance propulsive gas in the high gas speed therapeutic method to keep the adverse qi flowing downward.
Employing the present invention is that the gas of three phase solvents helps continuous extration method, makes organic matter to be separated or ionic species under the effect of bubble, can transmit between the liquid phase of three kinds of different densities; Especially under the situation of high gas speed, still can realize the no back-mixing operation of polymer phase and salt water, improve organic matter to be separated or ionic species simultaneously, accelerate mass transfer at polymer phase and organic solvent enriching rate mutually.In addition, the gas under the high gas speed of three phase solvents of the present invention helps continuous extraction equipment promptly can carry out intermittently operated, can realize serialization production again.Can under low gas velocity, operate, can be applicable to the operating condition under the high gas speed again.This equipment is equipped with liquid phase import and outlet at organic solvent phase, polymer phase, salt water, is provided with sample tap simultaneously, is convenient to detect solute concentration and changes in the air supporting process.Described device fabrication is convenient, installs, maintenance cost is lower.
Description of drawings
Fig. 1 is the structural representation that the three phase solvent gas of the present invention that comprise auxiliary equipment help continuous extraction equipment.
Reference numeral
1. phase mass-transfer zones in the middle of 2. times phase mass-transfer zones of air-flotation column 3.
4. go up the 6. salt water imports of phase mass-transfer zone 5. gas distributors
7. salt water outlet 8. has the dividing plate 9. polymer phase imports in hole
10. polymer phase exports 11. organic solvent phase imports, 12. organic solvents and exports mutually
13. salt water 14. polymer phases 15. organic solvent phases
16. filler 17. enlarges phase-separating section 18. spinner flowmeters
19. surge tank 20. gas cylinders 21. first thief holes
22. second thief hole 23. the 3rd thief hole 24. the 4th thief hole
25. the 5th thief hole 26 the 6th thief hole
The specific embodiment
To be further described specifically the present invention by specific embodiment below.
See also Fig. 1, a kind of three phase solvent gas help continuous extraction equipment to comprise that the bottom has the air-flotation column 1 (the air-flotation column internal diameter is 21mm, and length overall is 550mm) of gas access, further are provided with at the top of described air-flotation column 1 to enlarge phase-separating section 17; Described expansion phase-separating section 17 is the container of back taper, and the end opening of conical vessel and described air-flotation column 1 join, and the diameter suitable for reading of conical vessel is greater than the diameter of described air-flotation column 1.Described air-flotation column comprises following phase mass-transfer zone 2, middle phase mass-transfer zone 3 from the bottom to top successively and goes up mass-transfer zone 4 mutually, wherein, is filled with salt water 13 in the described following phase mass-transfer zone 2, contains organic matter to be separated or ionic species in the described salt water 13; Described down phase mass-transfer zone 2 comprises the salt water import 6 that is positioned at the gas distributor 5 of phase mass-transfer zone bottom down (it is that the aperture of G4 specification is 4～7 microns a sand core funnel that described gas distributor 5 adopts this areas model commonly used), is positioned at phase mass-transfer zone top down, is positioned at the salt water outlet 7 of phase mass-transfer zone bottom down; Be filled with polymer phase 14 in the phase mass-transfer zone 3 in described; Phase mass-transfer zone 3 comprises that the polymer phase of mass-transfer zone bottom exports 10 with being arranged in mutually in the polymer phase import 9 that is arranged in phase mass-transfer zone top in described; Described going up is filled with organic solvent phase 15 in the phase mass-transfer zone 4; The described phase mass-transfer zone 4 of going up comprises that the organic solvent of mass-transfer zone bottom exports 12 mutually with being positioned at mutually in the organic solvent phase import 11 that is positioned at phase mass-transfer zone top; Between described phase mass-transfer zone 2 down and the middle phase mass-transfer zone 3 dividing plate 8 that has the hole is installed also, this dividing plate that has the hole is a distribution grid with holes, and the aperture in the hole on the distribution grid with holes is 2mm, and percent opening is 30%; Be equipped with the quartz spring shape filler of phase mass-transfer zone 2 volumes 2～5% in accounting on the distribution grid with holes, the specification of quartz spring shape filler is that line directly is 1mm, and internal diameter 4mm, number of active coils are 6, and drift is 9mm.
The volume of described down phase mass-transfer zone 2 account for air-flotation column 1 cumulative volume 80%; In the volume of phase mass-transfer zone 3 account for air-flotation column cumulative volume 10%; The volume of last phase mass-transfer zone 4 account for air-flotation column 1 cumulative volume 10%.
One gas cylinder 20 is connected by the air inlet of pipeline with described surge tank 19, and the gas vent of surge tank 19 is connected by the described gas access of pipeline with described air-flotation column 1 bottom, and gas is provided in air-flotation column; On the gas vent of described surge tank 19 and pipeline that the described gas access of described air-flotation column 1 bottom is connected, spinner flowmeter 18 is installed, can further on this pipeline, installs valve additional simultaneously, and can be by spinner flowmeter 18 control gas flows.
The air-flotation column 1 of phase mass-transfer zone 4 is provided with first thief hole 21 on described; The air-flotation column 1 of phase mass-transfer zone 3 is provided with second thief hole 22 in described; On the air-flotation column 1 of described phase mass-transfer zone 2 down, be provided with the 3rd thief hole 23, the 4th thief hole 24, the 5th thief hole 25, the 6th thief hole 26 from top to bottom.
The gas that utilizes above-mentioned extraction equipment to carry out three phase solvents helps continuous extraction:
To carried out the research of air supporting three phase extraction as the multicomponent simulated wastewater system of organic matter o-nitrophenol to be separated and p-nitrophenol.Described salt water is made up of water and ammonium sulfate, and wherein the mass percentage concentration of the ammonium sulfate of salt aqueous phase is 25.74% (300g/L), and it is the aqueous solution of 50% polyethylene glycol that polymer phase adopts mass percentage concentration, and organic solvent is the n-hexane solvent mutually.O-nitrophenol and p-nitrophenol are about 200mg/L in the concentration of salt aqueous phase.Adopt 20wt.%H according to existing process conditions
2SO
4The pH value of regulating the salt aqueous phase system with 10wt.%NaOH is 4, and organic solvent phase: polymer phase: compare (volume ratio) of salt water is 1: 1: 8.
The concrete operations mode is: at first the aqueous solution that injects the ammonium sulfate that contains o-nitrophenol and p-nitrophenol by the import of salt water in the following phase mass-transfer zone of air-flotation column suspends charging near the distribution grid with holes; The aqueous solution that injects polyethylene glycol by the polymer phase import in the middle phase mass-transfer zone of air-flotation column is to assigned address then, the time-out charging; In the last phase mass-transfer zone of air-flotation column, inject the n-hexane solvent to assigned address by the import of organic solvent phase again, suspend charging; Open gas cylinder, regulating spinner flowmeter to gas speed is 40ml/min.
The described gas access of nitrogen from described air-flotation column bottom fed the air-flotation column, the nitrogen that feeds enters after by described sand core funnel in the aqueous solution of the described ammonium sulfate that contains o-nitrophenol and p-nitrophenol and carries out bubbling, the bubble that produces is carrying o-nitrophenol and p-nitrophenol upwards transmits, o-nitrophenol and p-nitrophenol be through the aqueous solution and the n-hexane solvent of described polyethylene glycol, and o-nitrophenol and p-nitrophenol are extracted in the aqueous solution of polyethylene glycol and in the n-hexane solvent; Help in the continuous extraction process at gas, every 10 minutes, the change in concentration of various solutes calculated solute distribution condition in each phase from each sample tap sample analysis three-phase.
The result shows, after air supporting extracts 30 minutes, the o-nitrophenol in the aqueous solution of ammonium sulfate and the concentration of p-nitrophenol remain unchanged substantially, the clearance of o-nitrophenol and p-nitrophenol reaches 82% and 81% respectively, and this moment, o-nitrophenol reached 793mg/L and 1007mg/L with p-nitrophenol respectively in polyethylene glycol concentration mutually.Continue extraction, extract after 70 minutes, the clearance of o-nitrophenol and p-nitrophenol reaches 86% and 83% respectively, the percentage that o-nitrophenol in the n-hexane solvent accounts for the o-nitrophenol total content reaches 60%, and the p-nitrophenol in the aqueous solution of polyethylene glycol accounts for 82% of p-nitrophenol total content.
After treating that the system extraction was stablized in 70 minutes, open the import of salt water, with in the described down phase mass-transfer zone not cracked ends salt solution export the identical flow of the aqueous solution of the ammonium sulfate that contains o-nitrophenol and p-nitrophenol after the raffinate of outflow mutually, by the import of salt water, in described phase mass-transfer zone down, replenish with former to descend pH value identical in the phase mass-transfer zone also be the aqueous solution of 4 the new ammonium sulfate that contains o-nitrophenol and p-nitrophenol with the speed of 20ml/min; With the identical flow of the aqueous solution of the polyethylene glycol after the raffinate that flows out of cracked ends polymer phase outlet not in the phase mass-transfer zone in described, by the polymer phase import, with the flow of 4ml/min in described, replenish in the phase mass-transfer zone with former middle phase mass-transfer zone in the aqueous solution of identical new polyethylene glycol; With the described identical flow of going up in the phase mass-transfer zone n-hexane solvent phase after the raffinate that cracked ends organic solvent not exports outflow mutually, by the import of organic solvent phase, with the flow of 4ml/min to described go up replenish in the phase mass-transfer zone with former last phase mass-transfer zone in identical new n-hexane solvent.Behind the aqueous solution of the aqueous solution of the intact new ammonium sulfate that contains o-nitrophenol and p-nitrophenol to be updated, new polyethylene glycol and the new n-hexane solvent, stablize sample analysis after 30 minutes, find that the aqueous solution of the aqueous solution of the new ammonium sulfate that contains o-nitrophenol and p-nitrophenol, new polyethylene glycol and the concentration of new n-hexane solvent remain unchanged, three phase solvent gas help continuous extraction to reach stable state, proceed three phase solvent gas and help continuous extraction.
By as seen above-mentioned, under the effect of distribution grid with holes and filler, reduced the back-mixing between salt water and the polymer phase, guaranteed that effectively under high gas speed three phase solvent gas help the stability of continuous extraction.
The three phase solvent gas of employing embodiment 1 help continuous extraction equipment and technology to carry out three phase solvent gas and help continuous extraction, difference wherein is: object to be separated is changed to ionic species by organic matter, polymer is changed to the EOPO block copolymer by polyethylene glycol, organic solvent is changed to the positive nonane solution of thioether by n-hexane, and polymer phase: organic solvent phase: compare (volume ratio) of salt water was changed to 1.5 by 1: 1: 8: .1.5: 7.
Described salt aqueous phase contains the binary composition that ionic species to be separated is Pd and Pt, system adopts the collecting reagent of the hydrochloric acid of 1mol/L as Pd and Pt, is mixed with Pd ion and Pt ion then and is saline solution about 100mg/L in the concentration of salt aqueous phase; It is the aqueous solution of 50% EOPO that described polymer phase adopts mass percentage concentration, and organic solvent is the positive nonane solution of thioether (the thioether volume fraction is 40%) mutually.
Be equipped with the bead filler of phase mass-transfer zone 2 volumes 2～5% in accounting on the distribution grid with holes, the diameter of bead is 2.5mm.
The concrete operations mode is: at first the aqueous solution that injects the ammonium sulfate that contains Pd ion and Pt ion by the import of salt water in the following phase mass-transfer zone of air-flotation column suspends charging near the distribution grid with holes; The aqueous solution that injects EOPO by the polymer phase import in the middle phase mass-transfer zone of air-flotation column is to assigned address then, the time-out charging; The positive nonane solution that injects thioether by the import of organic solvent phase in the last phase mass-transfer zone of air-flotation column is to assigned address again, the time-out charging; Open gas cylinder, regulate spinner flowmeter to gas speed and increase to 70ml/min gradually for 40ml/min.
The result shows, after air supporting extracts 30 minutes, the Pd ion in the aqueous solution of ammonium sulfate and the concentration of Pt ion remain unchanged substantially, the clearance of Pt ion and Pd ion reaches 90% and 81% respectively, and Pt ion and Pd ion can reach 336mg/L and 264mg/L respectively in the concentration of polymer phase.Continue extraction, be extracted into 70 minutes after, the percentage that the palladium ion in the positive nonane solution of thioether accounts for the palladium ion total content reaches 60%, the platinum ion in the aqueous solution of EOPO accounts for 78% of platinum ion total content.
After treating that system extraction 70 minutes is stable, open the import of salt water, with the speed of 20ml/min in described phase mass-transfer zone down, replenish with former under the aqueous solution of the identical new ammonium sulfate that contains Pt ion and Pd ion in the phase mass-transfer zone; With the flow of 4ml/min in described, replenish in the phase mass-transfer zone with former middle phase mass-transfer zone in the aqueous solution of identical new EOPO; Flow with 4ml/min replenishes in the phase mass-transfer zone and the former positive nonane solution of going up new thioether identical in the phase mass-transfer zone to described going up.Behind the positive nonane solution of the aqueous solution of the aqueous solution of the intact new ammonium sulfate that contains Pt ion and Pd ion to be updated, new EOPO and new thioether, stablize sample analysis after 30 minutes, the concentration of finding the positive nonane solution of the aqueous solution of the aqueous solution of the new ammonium sulfate that contains Pt ion and Pd ion, new EOPO and new thioether remains unchanged, three phase solvent gas help continuous extraction to reach stable state, proceed three phase solvent gas and help continuous extraction.
By as seen above-mentioned, under the effect of distribution grid with holes and filler, reduced the back-mixing between salt water and the polymer phase, guaranteed that effectively under high gas speed three phase solvent gas help the stability of continuous extraction.
Claims (10)
1. a phase solvent gas helps continuous extration method, it helps on the continuous extraction equipment at a kind of three phase solvent gas of use and carries out, it is characterized in that: described equipment comprises that the bottom has the air-flotation column of gas access, described air-flotation column comprises following phase mass-transfer zone, middle phase mass-transfer zone from the bottom to top successively and goes up mass-transfer zone mutually, wherein, be filled with the salt water in the phase mass-transfer zone under described, described salt aqueous phase contains organic matter to be separated or ionic species; Described down phase mass-transfer zone comprises the gas distributor that is positioned at phase mass-transfer zone bottom down, be positioned at phase mass-transfer zone top down the import of salt water, be positioned at the salt water outlet of phase mass-transfer zone bottom down; Be filled with polymer phase in the phase mass-transfer zone in described; The phase mass-transfer zone comprises that the polymer phase of mass-transfer zone bottom exports with being arranged in mutually in the polymer phase import that is arranged in phase mass-transfer zone top in described; Described going up in the phase mass-transfer zone is filled with the organic solvent phase; The described phase mass-transfer zone of going up comprises that the organic solvent of mass-transfer zone bottom exports mutually with being positioned at mutually in the organic solvent phase import that is positioned at phase mass-transfer zone top; Between described phase mass-transfer zone down and the middle phase mass-transfer zone dividing plate that has the hole is installed also;
The described gas access of gas from described air-flotation column bottom fed the air-flotation column, the gas that feeds enters described lower floor salt aqueous phase after by described gas distributor and carries out bubbling, the bubble that produces is carrying the organic matter described to be separated or the ionic species of described salt aqueous phase and is upwards transmitting, the organic matter to be separated of lower floor's salt aqueous phase or ionic species are through phase mass-transfer zone in described and the described mass-transfer zone mutually of going up, in the polymer phase of filling in the phase mass-transfer zone during the organic matter of lower floor's salt aqueous phase or ionic species are extracted to last mass-transfer zone mutually in the organic solvent of filling mutually in, finish three phase solvent gas and help the continuous extraction process;
The organic matter to be separated that described salt aqueous phase contains is a hydrophobic organic compound, and ionic species to be separated is inorganic metal ion or nonmetallic ion.
2. three phase solvent gas according to claim 1 help continuous extration method, it is characterized in that: help in the continuous extraction process at three phase solvent gas, with in the described down phase mass-transfer zone not cracked ends salt solution export the identical flow of the salt water after the raffinate of outflow mutually, constantly in described phase mass-transfer zone down, replenish the new salt water that contains organic matter to be separated or ionic species by the import of salt water; With the identical flow of the polymer phase after the raffinate that flows out of cracked ends polymer phase outlet not in the phase mass-transfer zone in described, by the continuous additional new polymer phase in the phase mass-transfer zone to described in of polymer phase import; With the described identical flow of going up in the phase mass-transfer zone organic solvent phase after the raffinate that cracked ends organic solvent not exports outflow mutually, constantly replenish new organic solvent phase in the phase mass-transfer zone to described going up by the import of organic solvent phase;
Described additional new organic matter to be separated is a hydrophobic organic compound, and ionic species to be separated is inorganic metal ion or nonmetallic ion.
3. three phase solvent gas according to claim 1 help continuous extration method, it is characterized in that: the volume of described down phase mass-transfer zone account for air-flotation column cumulative volume 60～80%; In the volume of phase mass-transfer zone account for air-flotation column cumulative volume 10～20%; The volume of last phase mass-transfer zone account for air-flotation column cumulative volume 10～20%.
4. three phase solvent gas according to claim 1 help continuous extration method, it is characterized in that: the speed of the gas of described feeding is smaller or equal to 80ml/min greater than 0ml/min.
5. three phase solvent gas according to claim 1 and 2 help continuous extration method, it is characterized in that: the salt water in the described down phase mass-transfer zone and down mutually in the mass-transfer zone additional new salt water form by water and inorganic salts, wherein the mass percentage concentration scope of the inorganic salts of salt aqueous phase is 20～40%;
Described inorganic salts are selected from one or more in sulfate, phosphate, the carbonate;
The new polymer phase that replenishes in polymer phase in described in the phase mass-transfer zone and the middle mass-transfer zone mutually is the aqueous solution of polymer, and wherein the mass percentage concentration of the polymer in the polymer phase is 40～60%;
Described polymer is selected from one or more in polyethylene glycol, polyethylene glycol-propane diols statistic copolymer, the polyethylene glycol-propane diols-polyethylene glycol three close block copolymers;
Described go up organic solvent in the phase mass-transfer zone mutually and in the last mass-transfer zone mutually additional new organic solvent be organic solvent mutually, described organic solvent is selected from C
6～C
12Alkane, aromatic hydrocarbons, alkane substitute, alcohol, ketone, ether, ester, phosphine, amine in one or more.
6. three phase solvent gas according to claim 5 help continuous extration method, it is characterized in that: described aromatic hydrocarbons is a kind of in benzene,toluene,xylene, the ethylo benzene;
Described alkane substitute is C
6～C
12A kind of in the halogenated alkane, halogen is F, Cl or Br;
Described alcohol is a kind of in octanol, the diethylhexyl alcohol;
Described ketone is a kind of in methyl iso-butyl ketone (MIBK), 2-heptanone, the cyclohexanone;
Described ether is a kind of in propyl ether, isopropyl ether, the butyl ether;
Described ester is a kind of in butyl acetate, amyl acetate, the methyl benzoate;
Described phosphine is a kind of in tributyl phosphate, di(2-ethylhexyl)phosphate (2-ethylhexyl) ester, 2-ethylhexyl phosphoric acid list (2-ethylhexyl) ester;
Described amine is a kind of in trioctylamine, trialkylamine, the chlorination trialkyl methylamine.
7. three phase solvent gas according to claim 1 and 2 help continuous extration method, it is characterized in that: described hydrophobic organic compound is selected from one or more in the phenol, halogenated hydrocarbons, halogenated aryl hydrocarbon of pigment, phenol, replacement; Described metal is selected from one or more among Fe, Cu, Ir, Rh, Cr, U, Co, Cd, Pd, the Pt; Described nonmetal be I, As or their mixture.
8. three phase solvent gas according to claim 7 help continuous extration method, it is characterized in that: the phenol of described replacement is nitrophenol, chlorophenol or their mixture;
Described halogenated hydrocarbons is C
6～C
12Halogenated aliphatic hydrocarbon, halogen is F, Cl or Br;
Described halogenated aryl hydrocarbon is halogeno-benzene or halogenated biphenyl, and halogen is F, Cl or Br.
9. three phase solvent gas according to claim 1 help continuous extration method, it is characterized in that: the described dividing plate that has the hole is distribution grid with holes or oscillating screen plate; The pore size in the hole on described distribution grid with holes or the oscillating screen plate is 1～3mm, and percent opening is 20～50%;
Described gas distributor is a sand core funnel.
10. three phase solvent gas according to claim 9 help continuous extration method, it is characterized in that: when the described dividing plate that has the hole is distribution grid with holes, be equipped with filler on the described distribution grid with holes, the filler of described laying accounts for 2～5% of middle phase mass-transfer zone volume; Described filler is bead or quartz spring shape filler.
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| US20230416867A1 (en) * | 2022-06-23 | 2023-12-28 | Virginia Tech Intellectual Properties, Inc. | Gas-assisted microflow extraction (game) system patent |
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| CN114618187B (en) * | 2022-02-28 | 2024-03-22 | 海南红塔卷烟有限责任公司 | Micro-bottle extraction device and method for thermogravimetric escaped matter analysis |
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