CN108546825B - The method that the useless trichotomy of solid waste liquid extracts olefinic carbon enrichment Rare Earth Separation inorganic material - Google Patents

The method that the useless trichotomy of solid waste liquid extracts olefinic carbon enrichment Rare Earth Separation inorganic material Download PDF

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CN108546825B
CN108546825B CN201810388920.3A CN201810388920A CN108546825B CN 108546825 B CN108546825 B CN 108546825B CN 201810388920 A CN201810388920 A CN 201810388920A CN 108546825 B CN108546825 B CN 108546825B
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rare earth
olefinic carbon
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solid waste
trichotomy
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CN108546825A (en
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曹晏
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Shanxi Zhong Spectrum Energy Technology Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0038—Obtaining aluminium by other processes
    • C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The present invention, which is especially, discloses a kind of method that the useless trichotomy of solid waste liquid extracts olefinic carbon enrichment Rare Earth Separation inorganic material, and the present invention is with overcritical ScCO2/H2Based on O/ alicyclic organic three-phase extraction system, it is aided with the reinforcings such as stirring, microwave, ultrasound or heating or appropriate acid adding and extracts and strengthen the means such as mass transfer, removed when necessary using mechanical forces such as high speed ball millings and strengthen the fracture of chemical bond and be re-engaged, ScCO2Phase and H2O matches to form rare earth and carbonaceous in overcritical, acidic environment dissociation solid waste, and alicyclic organic analog assistant and the rare earth of safety and environmental protection are complexed, and extraction is dissolved in H2The rare earth of O phase, and porous carbon or graphene carbon remain substantially in H2In O, rare earth is transferred to CO when organic ester is identical2Stable CO is formed in phase2Solution phase is extended, to change distribution coefficient of the solute in two-phase, completes the separation and Extraction of rare earth element and olefinic carbon.

Description

The method that the useless trichotomy of solid waste liquid extracts olefinic carbon enrichment Rare Earth Separation inorganic material
Technical field
The invention belongs to coal base field of solid waste disposal, and it is dilute to extract olefinic carbon enrichment more particularly to a kind of useless trichotomy of solid waste liquid The method of soil separation inorganic material.
Background technique
China be in the world maximum coal mining, coal electricity and coal chemical industry production state, coal production, processing and consumption A large amount of solids, liquid wastes can be generated in the process, great burden is caused to environment, and the yield of such as 2015 China's flyash is high Up to 6.2 hundred million tons, cumulative amount over the years is bigger, and not in time, the coal base waste material of proper treatment can threaten to environment and human survival. National policy supports that the combustion power generation of colm and gangue is to respond actively, while actively pushing forward various solid wastes energetically at present It is about 60% using useless means, the comprehensive utilization ratio of China's solid waste such as administer of, liquid, wherein flyash is mainly used for building building cement original The fields such as material, foundation engineering filler, agromelioration and waste water, waste gas pollution control and treatment, specific use include that cenosphere extracts, is resistance to Fiery material and synthetic zeolite etc..It is big that conventional use eats ash quantity, but economic value is low, purposes is limited.Coal base solid waste, liquid are useless to be rich in Aluminium, silicon, carbonaceous and it is other provide the element utilized, and with pyrogene coal supply steel, nonferrous smelting industry and generate solid waste, liquid Useless ingredient more horn of plenty and complexity, clear flyash has the potentiality of extractable high value added product, such as rare earth noble metal.
Rare earth is known as " the industrial vitamin " of 21 century new material, has unique light, electricity, magnetic and catalytic performance, generation Expenditure is low, is emerging high-tech sector, national defense construction and the important foundation strategic materials rebuild traditional industry.Rare earth is that country is green The development of color technology provides raw material support, and emerging market demand is huge.In national proposition industry focus new energy (photovoltaic technology etc.), New-energy automobile (energy-storage system, motor body) and new material (semiconductor lighting material, new function material).Advanced carbon simultaneously Material also provides raw material support for the development of national green technology, and emerging market demand is huge.Advanced carbon material includes high quality Graphite, the porous carbon and novel olefinic carbon for crystallizing regular pore structure prosperity.Graphite is the necessary raw material in many essential industry fields, Porous carbon is the electrode base material of supercapacitor, lithium battery, and the appearance of graphene more makes field of new materials leap, and is caused complete Ball research boom.Graphene raw material be generally natural graphite and petroleum coke and anthracite production graphite raw material, production process by First resource limitation, and graphitizing process temperature condition (usually 2400 DEG C) is harsh and energy consumption is high.
Coal base solid waste or liquid, which give up, and steel nonferrous smelting industry solid waste liquid is useless is expected to become its new secondary resource, but mesh It is preceding not yet to form apparent intersection, pay attention to, earlier layout is extracted with coal base solid waste and is enriched with advanced carbon material and rare earth element body The perspective of technology development is showed.Existing research shows that there are extractible graphene quantum dot, coal knots in the molecular structure of coal Crystalline carbon in structure is easier to be oxidized substitution, can be applied to the fields such as optical electro-chemistry, biomedicine.The solid waste of gasification system Universal carbon content is high in residual coke, and flyash carbon content is lower, and flying dust yield is huge, and the absolute quantum of output of carbon is considerable, in addition Not separating to it can have an adverse effect to conventional utilize of flyash.These carbon residues experienced pyroprocess, be graphitized journey Du Genggao, carbon structure tend to regular homogenization, the potential graphite presoma for becoming source considerable, again to graphene carbon raw material. Coal is a kind of solid mixture of structure composition complexity simultaneously, and rare earth, noble metal containing a variety of low concentrations, some have reached companion Raw deposit scale simultaneously develops and uses, and since coal mining total amount is huge, coal base solid waste is separating carbonaceous, directly extracts olefinic carbon and rare earth And the inorganic elements such as sial are recycled, by the resource value that waste is substantially improved, extend Coal Industrial chain；Using coal base industry as Rare earth, noble metal another emerging source have great strategic significance.The molten boiling point of rare earth element is higher, by burning of coal or gas Change process can be enriched with into the coals base solid waste such as coal ash, coal tar, not need traditional rare earth ore mining mine and decomposition step, can directly simultaneously Enter the refining stage of traditional rare earth, therefore be expected to reduce pollution, reduce the destruction to ecology, to promote coal base solid waste Extraction of rare eart Economic feasibility provide foundation.It is restricted by state of the art, in recovery rate, energy consumption, material consumption, environmental protection and operability etc. Aspect existing defects, main acid-base method subsequent processes problem is more, the basic research of some innovations, such as ionic liquid, absorption Agent method and light conversion method, face after high expensive, extraction that grade is low, the problems such as separating again, it is more difficult to which support is easily accept by enterprises for Suitable Industrialized processing technique scheme.
In addition in view of really minable rich Rare Earth Mine is few at present, to the solid waste generated in its process production process, The useless recycling of liquid is the only way which must be passed to the effective exploitation of resource.Meanwhile Extraction of rare eart process established at present is related to mining, divides Solution and purification three steps of refining are decomposed there are many common problems, as high temperature and high energy consumption, a large amount of water consumptions, soda acid and strong pollution help Agent, generates a large amount of waste water and dregs, and concomitant radioactivity " thorium " pollutes waste residue, has very strong contamination characteristics to environment, to prior art Transformation it is also imperative.
Supercritical fluid due to its special physicochemical property, stabilization, it is pollution-free the features such as, catered to modern industry and chased after The theories such as safe and environment-friendly asked.Wherein supercritical CO2(ScCO2) nontoxic, odorless, fire-retardant, from a wealth of sources, inexpensive, have relatively Low critical-temperature and pressure (304.1K, 7.38 MPa), since the boundary of gas and liquid two phases disappears, the biography of generating process therebetween Matter speed about 2 orders of magnitude faster than liquid, physicochemical properties (viscosity, dielectric constant, diffusion coefficient and solvability) are to temperature Degree, especially pressure are very sensitive, can regulate and control lock out operation by adjusting pressure and temperature.It is organic that this becomes tradition The green substitute of solvent is to study most commonly used supercritical fluid at present, but there is no extract for various solid wastes in the world Precedent.
Currently, Hummers method is to prepare the main method of graphene oxide using high purity graphite as raw material wet process, further Graphene can be obtained in reduction, but this method destroys greatly the conjugated structure of graphene, is only limitted to non-electronics major application, together When need strong acid and strong oxidizer, severe reaction conditions have stronger pollution to environment.Existing research shows preferably to remove The solvent surface tension of graphene is 40 ~ 50mJ/m2.Supercritical fluid meets graphene stripping conditions, and low-viscosity, low surface Tension, high diffusion coefficient and good surface wettability become the good solvent for infiltrating and expanding between stratified material.ScCO2It inserts The method of layer preparing graphite alkene, reduction of blood pressure in high-speed removes graphite expansion, easy to operate, at low cost, does not introduce in the process Other chemical functional groups and the perfect lattice structure and high conductivity that ensure that graphene.
Summary of the invention
The present invention overcomes existing coal base solid waste extracting method recovery rate low, energy consumption, material consumption height and the low problem of operability, There is provided a kind of solid waste, liquid gives up the method that trichotomy extracts olefinic carbon, enrichment rare earth, separates inorganic material.The present invention is with coal base solid waste Or liquid is useless, steel nonferrous smelting industry solid waste liquid is useless and rare earth ore concentrate or slag or liquid give up for basic raw material, with overcritical ScCO2/H2Based on O/ alicyclic organic three-phase extraction system, the materials such as olefinic carbon and rare earth noble metal are extracted, are seldom related to acid in the process Alkali, separation can be realized in the process, short route, system is environmental-friendly, product is diversified, therefore technology is easily implemented, risk is easy to Control improves recovery rate, and energy consumption, material consumption are low.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows: the useless trichotomy extraction olefinic carbon of solid waste, liquid, The method for being enriched with rare earth, separating inorganic material, follows the steps below:
Raw material to be processed is mixed into water by step 1), is then added to supercritical CO2Reaction kettle in, maintain the temperature of reaction kettle For 283K-423K, pressure 3.5MPa-35MPa, the Extraction of rare earth element from the raw material of addition, while olefinic carbon being removed；
Step 2 is separated by solid-liquid separation the solution after reaction, and isolated solid is large sial solid material；
Step 3) reduces and maintains the temperature of reaction kettle for 283K-373K, pressure 0.1MPa-10MPa, in a kettle Dissolvable sulfide or thioacetamide or copper reagent is added, by alkali metal, alkaline-earth metal, transition metal and heavy metal ion Olefinic carbon and rare earth are detached from precipitation and separation, with blended liquid phase；
Then organic ester molecule is added in step 4) in a kettle, organic ester molecule and rare earth form solvated complex, Olefinic carbon stays in H2O phase, organic ester molecule and CO2It dissolves each other to form uniform phase gas-expanded liquids, gas-expanded liquids are with water phase Layering, it is operated by liquid separation, by the gas-expanded liquids with organic ester molecule rare earth solvated complex and alkene can be contained The H of carbon2O phase separates, and the gas-expanded liquids with organic ester molecule rare earth solvated complex are sent into rare earth element and are extracted Storage tank；
Step 5) to rare earth element extract storage tank carry out reduced pressure treatment temperature be 273K-373K, pressure 0.1MPa- 9MPa, CO2It is separated with rare earth, organic ester molecule rare earth solvated complex, the CO of recycling2Step 1) reuse is returned again to, is had Machine ester molecule pickling Extraction and enrichment rare earth, while separating and recovering organic ester molecule；
Step 6) is to the H containing olefinic carbon in reaction kettle2O phase carries out olefinic carbon extraction process to obtain olefinic carbon.
Further, the raw material to be processed is gangue, or is colm, or be flyash or be coal tar；Or to wash Coal works generates waste water or is coal tar；Or it can be related to all metallurgy industry production processes for steel nonferrous smelting industry solid waste The solid waste or liquid of middle generation are useless, and rare earth ore concentrate or slag or liquid give up as Rare Earth Mine itself or produce after having been subjected to other methods extractions Raw rare earth slag or liquid are useless.
Further, it is provided with agitating device on the reaction kettle in the step 1), during the reaction by stirring Means.
Further, organic ester molecule in step 4) is neutral orthophosphoric acid extractant.
Further, the neutral orthophosphoric acid extractant is tbp ((C4H9O)3It PO), or is three n-octyl oxygen Change phosphorus ((C8H17)3PO).
Further, it can be mentioned during entire or stepwise reaction with assisted microwave synthesis, ultrasound or heating or appropriate acid adding reinforcing Take and strengthen mass transfer means, or the means increasing strengthening the fracture of chemical bond using the mechanical force removing of high speed ball milling and being re-engaged Strong reaction effect.
Further, the olefinic carbon extraction process in step 6) is to be filtered or used 100- using 0.1-10 Mm filter film The dialyser of 10000 dalton carries out dialysis or rotates the H containing olefinic carbon with revolving speed 2000-50000r/min high speed centrifugation2O Mutually obtain olefinic carbon.
The present invention has the advantages that compared with prior art.
1, the great demand of country that the present invention generates high value added product using the resource utilization of solid waste generates high as background Value-added product includes enrichment of rare earth elements, porous carbon material, the direct products of class graphene carbon sheet layer material or secondary original Material, product end remarkable in economical benefits is extensive with prospect, supports the material supply of new industry and new energy.
2, the coal base solid waste main object that the present invention is handled is the cinder of Chemical Industry (coal gasification), large power station powder Coal ash, colm, gangue and coal washing waste water form the technology solid waste of radiation-curable to great metallurgy industry and dilute simultaneously The waste residue etc. generated in the existing concentrate of soil and abandoned mine or conventional rare production, raw material supply is abundant, plays protection to rare mineral Or deposit effect, reduce the environmental burden of related industry indirectly.
3, the present invention relates to the adjustable supercritical carbon dioxide/water/organic ester systems of safe and environment-friendly, mild condition to coal The extraction of base solid waste is removed, the key technology of isolation integral, and target is enrichment rare earth, is taken into account and is obtained olefinic carbon material and divided silicon Aluminium inorganic material.Technology path embodies low water consumption, discharges without soda acid operation, without ammonia nitrogen, extracts, removes, separating step is by simple Critical technical parameter regulates and controls (CO2Temperature and pressure), embodiment green, the theory of short route, by-product high value added product, and meanwhile it is innoxious solid Useless processing.
3, the few soda acid of whole process of the invention, can be realized that separation, short route, system are environmental-friendly, produce in the process Object diversification, therefore technology is easily implemented, risk is easily controllable.
4, tradition extract pure olefinic carbon effect it is single, be added other elements to its hydridization be its performance boost means it One, distinctive hybridizing elements itself and process conditions of the invention, which can be realized, in coal base solid waste of the invention extracts the straight of olefinic carbon Hydridization is connect, while can also reduce the requirement to raw material supply and process separation.
Detailed description of the invention
The present invention will be further described in detail with reference to the accompanying drawing.
Fig. 1 is flow diagram of the invention.
Specific embodiment
As shown in Figure 1, solid waste, liquid give up trichotomy extract olefinic carbon, enrichment rare earth, separate inorganic material method, according to Lower step carries out:
(coal base solid waste material or liquid are useless, steel nonferrous smelting industry solid waste liquid gives up and rare earth ore concentrate by raw material for step 1) Or slag or liquid give up) it is mixed into water, it is then added to supercritical CO2Reaction kettle in, maintain reaction kettle temperature be 283K-423K, Pressure is 3.5MPa-35MPa, the Extraction of rare earth element from the raw material of addition, while olefinic carbon being removed；
Step 2 is separated by solid-liquid separation the solution after reaction, and isolated solid is large sial solid material；
Step 3) reduces and maintains the temperature of reaction kettle for 283K-373K, pressure 0.1MPa-10MPa, in a kettle Dissolvable sulfide or thioacetamide or copper reagent is added, by alkali metal, alkaline-earth metal, transition metal and heavy metal ion Olefinic carbon and rare earth are detached from precipitation and separation, with blended liquid phase；
Then organic ester molecule is added in step 4) in a kettle, organic ester molecule and rare earth form solvated complex, Olefinic carbon stays in H2O phase.Organic ester molecule and CO2It dissolves each other to form uniform phase gas-expanded liquids, gas-expanded liquids are with water phase Layering, it is operated by liquid separation, by the gas-expanded liquids with organic ester molecule rare earth solvated complex and alkene can be contained The H of carbon2O phase separates；
Step 5) to rare earth element extract storage tank carry out reduced pressure treatment temperature be 273K-373K, pressure 0.1MPa- 9MPa, CO2It is separated with rare earth, organic ester molecule rare earth solvated complex, the CO of recycling2Return again to step 1) reuse；Have Machine ester molecule pickling Extraction and enrichment rare earth, while separating and recovering organic ester molecule；；
Step 6) is to the H containing olefinic carbon in reaction kettle2O phase carries out or filters (0.1-10 Mm filter film), crosses dialysis (using the dialyser of 100-10000 dalton) or high speed centrifugation (revolving speed 2000-50000) can separate olefinic carbon.
As shown in Figure 1, the technological subject of this method is an autoclave, temperature, pressure can under the reaction of setting The bound of adjustable extent is adjusted and reserved, corollary system, CO are controlled2Compressibility, heating furnace and control condition monitor system, And default liquid (organic ester phase and surfactant) mechanism is added and liquid phase excludes mechanism.System attachment mainly include three can The component directly purchased visits rifle for microwave office, ultrasound and transmitting and can push ball grinding stirring system.System further includes that liquid is broken admittedly Cream, separation, CO2Release room and high-pressure chromatographic column room.
Complete olefinic carbon material and Extraction of rare eart in the reaction kettle of total system, accessory system to extract reaction process strengthen, Regulation is consolidated, in liquid at cream, break milk separation and CO2Release room completes rare earth complex, transfer and concentration.The monitoring unit pair of system The control of this technology is most important, controls reaction chamber in CO with this2The phase and composition of three-phase or mixed phase under pressurized conditions, separately It outside include the electrochemical electrode test fittings of some conventional temperature, pressure, pH and sensitive online purpose, convenient for better Monitoring, the key parameter for understanding system phase.As the further extension of this technology, rare earth point is completed in high-pressure chromatographic column room From exploring hollow-fibre membrane stationary phase ester liquid film method, promote to realize economical without demulsification process ester, aqueous phase separation, utilize polymerization The lipophilicity of object is adsorbed on organic ester mutually in micropore with capillarity to form discontinuous phase.
The operation principle of the present invention is that: ScCO2Itself is nonpolarity, does not directly pretend use to metal ions such as rare earths, but In ScCO2Middle addition H2O can form high concentration carbonic acid, pH reduced with temperature and pressure rise and reduce (such as in temperature 293K, Pressure is under 5MPa, and system pH just can reach the inorganic acid that 3.19) can be substituted in the extraction of coal base solid waste, and H2O phase It is reacted in the presence of can also accelerate to extract, the olefinic carbon of removing and the rare earth of extraction and other heavy metals can be present in ScCO2/H2O phase, Only need simple solid-liquor separation that can obtain large sial solid material in advance.But sial component is in ScCO2/H2O phase may be sent out First portion hydrolysis, carbonation are influenced by the factors such as kinetics and film forming cladding, determine final specific form.
Then ScCO after isolation2/H2Dissolvable sulfide (Na is added in O blended liquid phase2S), thioacetamide or copper examination Agent can make heavy metal ion precipitation and separation by acidic environment therein, be detached from olefinic carbon in blended liquid phase and rare earth.
The small ScCO of polarity2The affinity not strong to rare earth element is not easy to promotion and H2The rare earth ion that O phase is affine From H2It is separated in O phase.In ScCO2/H2In O mixed phase further be added tendency with rare earth formed complexing environmental protection mildly it is organic Ester molecule (molten neutral orthophosphoric acid extractant, such as tbp, three n-octyl phosphorous oxides etc. with shipwreck), in ScCO2With H2O Under the acidic environment of mixed phase, so that neutral phosphoric acid extraction agent and rare earth is formed solvated complex, squeeze out the water of rare earth hydrate Molecule, and increase the molecular volume of extract.Extraction reaction may be expressed as:
REE3+ +3X—+ pS (0) REEX3Sp(0)
Wherein S is extractant, X -=NO3-, Cl-, SCN-, ClO4-。
Extractant organophosphorus ester polarity is small, is insoluble in H2O, but and CO2It can dissolve each other to form uniform phase gas-expanded liquids (GXLs), such rare earth element can be eventually transferred into organophosphorus ester/CO2Uniform mixed phase in, promote reaction after rare earth Metallic product and the H containing carbene2O phase separates.
Extraction process can be carried out quickly, depending on three features of existing system, one is ScCO2With close to gas The viscosity of body, relative to liquid H2O diffusion coefficient is much bigger, and surface tension is small, mobility and good penetrability, has good Mass transfer ability.
Second, the neutral phosphor acids extractant of longer alkyl chain will form supercritical CO2Microemulsion, nonpolar tail end stretching, extension In supercritical CO2Phase, polarity head end are gathered into polarity core, and hydrone is solubilized into micro emulsion core, are formed carbon dioxide Bao Shui (W/C) Microemulsion it is extracted in water phase, numerous surface is greatly micro- so that extractant is complexed with rare earth ion First " extraction reactor " promotees extraction and accelerates.Since water phase is wrapped in extractant, rare earth ion is not exposed to ScCO2System In, without influencing extraction yield because forming carbonate deposition.
Third, due to H2There are the Al ion of the Na ion being added early period and possible solid waste dissolution, their hydrations to make for O phase With a part of free water molecule is attracted, it increase accordingly rare earth effective concentration in water phase, this effect is equally applicable to largely Existing anion, two kinds of effects can greatly improve distribution ratio of the rare earth in extractant, improve extraction yield.Adjust CO2 temperature Pressure can also be such that organic ester solvent expands, and cohesion can significantly reduce, and solvability reduces, the rare earth knot in facilitated extraction agent Brilliant or amorphous sediment.ScCO2It is very sensitive to the change of state parameter, in the minor change of Near The Critical Point temperature and pressure It will make the property of fluid that biggish change occur.It therefore, can be by the temperature and pressure of control system come control system Dissolution characteristics, mass transfer and heat-transfer character and response feature simultaneously realize separation.
Finally in CO2Organic ester molecule, H are recycled after decompression2O solution can restore to neutrality, omit alkali neutralization post-processing step Suddenly, the high energy consumption of water treatment procedure is eliminated.Process intensification can be by ultrasound, stirring, ball milling and microwave etc..
Technology path of the invention is with ScCO2/H2Based on O/ alicyclic organic three-phase extraction system, it is aided with microwave, ultrasound or heating Mass transfer means are extracted in equal reinforcings, are removed when necessary using mechanical forces such as high speed ball millings and are strengthened the fracture of chemical bond and be re-engaged. ScCO2Phase and H2O match to be formed acidic environment dissociation solid waste in rare earth and carbonaceous, the alicyclic organic analog assistant of safety and environmental protection with it is dilute Soil is complexed, and extraction is dissolved in H2The rare earth of O phase, and porous carbon or graphene carbon remain substantially in H2In O.Organic ester mutually can It is transferred to CO2Stable GXLs phase is formed in phase, to change distribution coefficient of the solute in two-phase, complete rare earth element with The separation and Extraction of olefinic carbon.
The embodiment of the present invention is explained in detail above in conjunction with attached drawing, but the present invention is not limited to above-mentioned implementations Example, within the knowledge of a person skilled in the art, can also make without departing from the purpose of the present invention Various change out.

Claims (7)

  1. The method that trichotomy extracts olefinic carbon enrichment Rare Earth Separation inorganic material 1. solid waste liquid gives up, which is characterized in that according to following step It is rapid to carry out:
    Raw material to be processed is mixed into water by step 1), is then added to supercritical CO2Reaction kettle in, maintain the temperature of reaction kettle to be 283K-423K, pressure 3.5MPa-35MPa, the Extraction of rare earth element from the raw material of addition, while olefinic carbon being removed；
    Step 2 is separated by solid-liquid separation the solution after reaction, and isolated solid is large sial solid material；
    It is 283K-373K that step 3), which reduces and maintain the temperature of reaction kettle, and pressure 0.1MPa-10MPa is added in a kettle Dissolvable sulfide or thioacetamide or copper reagent and mix alkali metal, alkaline-earth metal and transition metal precipitation and separation Olefinic carbon and rare earth are detached from liquid phase；
    Then organic ester molecule is added in step 4) in a kettle, organic ester molecule and rare earth form solvated complex, olefinic carbon Stay in H2O phase, organic ester molecule and CO2It dissolves each other to form uniform phase gas-expanded liquids, gas-expanded liquids and water phase are layerings , it is operated by liquid separation, by the gas-expanded liquids with organic ester molecule rare earth solvated complex and olefinic carbon can be contained H2O phase separates, and the gas-expanded liquids with organic ester molecule rare earth solvated complex are sent into rare earth element and extract storage tank；
    Step 5) extracts storage tank to rare earth element and carries out reduced pressure treatment, temperature 273K-373K, pressure 0.1MPa-9MPa, CO2 It is separated with rare earth, organic ester molecule rare earth solvated complex, the CO of recycling2Return again to step 1) reuse, organic ester point Sub- pickling Extraction and enrichment rare earth, while separating and recovering organic ester molecule；
    Step 6) is to the H containing olefinic carbon in reaction kettle2O phase carries out olefinic carbon extraction process to obtain olefinic carbon.
  2. The method that trichotomy extracts olefinic carbon enrichment Rare Earth Separation inorganic material 2. solid waste liquid according to claim 1 gives up, Be characterized in that: the raw material to be processed is gangue, or is colm, or be flyash or be coal tar；Or it is generated for coal washery Waste water or for coal tar or be Rare Earth Mine itself or to have been subjected to the rare earth slag generated after other methods are extracted or liquid it is useless.
  3. The method that trichotomy extracts olefinic carbon enrichment Rare Earth Separation inorganic material 3. solid waste liquid according to claim 1 gives up, It is characterized in that: being provided with agitating device on the reaction kettle in the step 1), during the reaction by the means of stirring.
  4. The method that trichotomy extracts olefinic carbon enrichment Rare Earth Separation inorganic material 4. solid waste liquid according to claim 1 gives up, Be characterized in that: organic ester molecule in step 4) is neutral orthophosphoric acid extractant.
  5. The method that trichotomy extracts olefinic carbon enrichment Rare Earth Separation inorganic material 5. solid waste liquid according to claim 4 gives up, Be characterized in that: the neutrality orthophosphoric acid extractant is tbp, or is three n-octyl phosphorous oxides.
  6. The method that trichotomy extracts olefinic carbon enrichment Rare Earth Separation inorganic material 6. solid waste liquid according to claim 1 gives up, It is characterized in that: can be strengthened during entire or stepwise reaction with assisted microwave synthesis, ultrasound or heating or acid adding and extract and strengthen mass transfer Means, or the means intensified response effect strengthening the fracture of chemical bond and being re-engaged is removed using the mechanical force of high speed ball milling.
  7. The method that trichotomy extracts olefinic carbon enrichment Rare Earth Separation inorganic material 7. solid waste liquid according to claim 1 gives up, Be characterized in that: the olefinic carbon extraction process in step 6) is to be filtered or used 100-10000 dongle using 0.1-10 Mm filter film The dialyser to pause carries out dialysis or rotates the H containing olefinic carbon with revolving speed 2000-50000r/min high speed centrifugation2O phase obtains alkene Carbon.
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