CN104561613B - The process in yttrium richness europium ore deposit in a kind of Nd/Sm～Dy/Ho packet separation - Google Patents
The process in yttrium richness europium ore deposit in a kind of Nd/Sm～Dy/Ho packet separation Download PDFInfo
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Abstract
The process in yttrium richness europium ore deposit in a kind of Nd/Sm～Dy/Ho packet separation, with P507 for rare-earth extractant, with middle yttrium richness europium ore deposit for raw material, 3rd outlet is located at two and is entered the three extraction sections of washing going out fractional extraction system, is provided with the N235 extraction acid section for extracting acid agent, TBP is demulsifier between washing section and stripping section; Hydrionic side effect is eliminated by the extraction acid effect of N235. Compared with being grouped separating technology with existing middle yttrium richness europium ore deposit Nd/Sm～Dy/Ho, the acid and alkali consumption of Rare Earth Separation technical process being greatly lowered, wherein alkaline reagent consumption declines 58.2%～64.5%, and the consumption of hydrochloric acid declines 22.7%～34.2%; The wastewater discharge of rare-earth extraction separating process process is greatly reduced, and the green degree of Rare Earth Separation increases substantially; Extraction tank progression can reduce 12.7%～22.2%, and the gross investment of rare-earth extraction separating process declines; The quality of heavy rare earth product is improved.
Description
Technical field
The present invention relates to the process in yttrium richness europium ore deposit during a kind of Nd/Sm～Dy/Ho packet separates, particularly relate to phosphonate ester P507 be rare-earth extractant, N235 is for hcl as extraction agent agent, two enter three goes out yttrium richness europium ore deposit during fractional extraction system separates, and fractional extraction system middle rare earth extraction quantity is not less than the process of Nd/Sm～Dy/Ho packet rare-earth separating of rare-earth sodium saponification amount. The invention belongs to the solvent extraction field in hydrometallurgy.
Background technology
Middle yttrium richness europium ore deposit is the ion adsorption type rare earth ore that reserves are maximum, and the content of its LREE La～Nd is about 55%, and the content of rare earth elements Sm～Dy is about 15%, and the content of heavy rare earth element Ho～Lu and Y is about 30%. It follows that the light middle heavy rare-earth element content in middle yttrium richness europium ore deposit is comparatively uniform, and middle heavy rare-earth element content is of a relatively high. Therefore, middle yttrium richness europium ore deposit is extremely important rare earth resources.
The acid and alkali consumption of rare earth full-separating process flow process is had decisive influence by first time cutting, and therefore first time is cut into the cardinal task of the design of Rare Earth Separation flow process, selection and optimization. At present, the best first time in middle yttrium richness europium ore deposit is cut into P507 extracting and washing section aqueous phase three and exports～Nd/Sm～Dy/Ho～packet separating technology. Compared with two traditional outlet process, this three outlet separation process scheme can save substantial amounts of acid and alkali consumption. But, the present invention furthers investigate discovery, and existing rare-earth fractionation extraction and separation technology all exists various shortcoming, P507 extracting and washing section aqueous phase three exports～Nd/Sm～Dy/Ho～packet separate in yttrium richness europium miner's skill, no exception. For extract and separate, the three outlet fractionation extraction process in existing middle yttrium richness europium ore deposit are primarily present following three big problems.
First, extraction quantity is big. Middle heavy rare earth Sm～Lu and Y all extracts into organic facies in extraction section, it means that need to consume more saponification caustic (alkaline reagent such as sodium hydroxide or ammonia).
Second, washing amount is big. 3rd exported product Sm～Dy enriched substance (containing a certain amount of Ho～Lu and Y) must be washed at washing section, it means that needs to consume more washing hydrochloric acid.
3rd, hydrion side effect is serious. Hydrion also produces some side effect being unfavorable for Rare Earth Separation rising while cleaning function, mainly has: 1) hydrogen ion concentration increase causes that separation declines, washing section end is particularly evident; 2) hydrion washing rare earth extraction amount is lower than the phenomenon of rare-earth sodium saponification amount (i.e. underload phenomenon), and washing section end is particularly acute; 3) hydrionic cleaning function needs just to complete (namely owing washing phenomenon) in the even whole washing section of the some levels of washing section, causes that separation efficiency reduces, is embodied in stage efficiency and reduces; 4) washing acid must be excessive, and this not only to consume more washes acid, and can strengthen the amplitude that Rare Earth Separation coefficient declines; 5) when hydrogen ions to the 1st grade, not only directly waste saponification caustic, and reduce the treating capacity of rare-earth fractionation extraction and separation technology system. Therefore, the side effect that hydrion produces at washing process so that the stage efficiency of rare-earth fractionation extract and separate declines, progression increases, acid and alkali consumption amount increases, and separation costs raises.
Sum it up, existing middle yttrium richness europium ore deposit～Nd/Sm～Dy/Ho～packet separating technology still exists, acid-base reagent consumption is relatively big, extraction progression is more, the more high deficiency of separation costs.
Summary of the invention
It is an object of the invention to have that acid-base reagent consumption is relatively big for existing middle yttrium richness europium ore deposit～Nd/Sm～Dy/Ho～packet separating technology, more, the more high deficiency of separation costs that extracts progression, yttrium richness europium miner's process during a kind of new Nd/Sm～Dy/Ho packet separates is proposed, enter three by two and go out fractional extraction technology reduction extraction quantity and washing amount, the side effect of hydrion washing is eliminated, it is achieved reduce yttrium richness europium ore deposit fractional extraction stage efficiency in the acid and alkali consumption of Rare Earth Separation, raising, reduce the cost of Rare Earth Separation by extracting acid section.
The process in yttrium richness europium ore deposit in a kind of Nd/Sm～Dy/Ho packet separation of the present invention, with the rare earth chloride solution in middle yttrium richness europium ore deposit for feed liquid, the extraction section of the washing aqueous phase of fractional extraction system is located in 3rd outlet, is provided with the extraction acid section being demulsifier for extraction acid agent, tributyl phosphate (TBP) with tertiary amine N 235 between washing section and stripping section; Utilize the extraction acid effect of N235 to enter three with yttrium richness europium ore deposit two in realizing to go out fractional extraction system middle rare earth extraction quantity and be not less than rare-earth sodium saponification amount.
Present invention process scheme is as follows:
1) rare earth feed liquid
With the rare earth chloride solution in middle yttrium richness europium ore deposit for feed liquid, rare earth feed liquid middle rare earth concentration is 1.0M～1.5M, and pH value is 1～3. Middle yttrium richness europium ore deposit rare earth feed liquid is divided into two parts; In rare earth element, the light rare earth molar fraction in first part of rare earth feed liquid is not less than the light rare earth molar fraction in second part, and namely the middle heavy rare earth molar fraction in second part of rare earth feed liquid is not less than the middle heavy rare earth molar fraction in first part.
2) rare earth extraction organic facies
Rare earth extraction organic facies is kerosene or the sulfonated kerosene solution of P507, and the concentration of volume percent of P507 is 30%～45%; Adding fractional extraction system with light rare earth (La～Nd) saponification organic facies form, saponification degree is 30%～40%.
3) cleaning mixture
Cleaning mixture is the solution of heavy rare earth element (Ho～Lu and Y), and its rare earth concentration is 0.72M～0.99M, and pH value is 1～4.
4) fractional extraction system
Fractional extraction system is two enter three and go out fractional extraction system, is made up of extraction section, the extraction section of washing and washing section, and the extraction section of washing aqueous phase is located in the 3rd outlet, and the extraction section of washing is divided into the forward extraction section of washing and the rear extraction section of washing by the 3rd outlet.Light rare earth saponification organic facies enters fractional extraction system from the 1st grade of extraction tank; First part of rare earth feed liquid enters fractional extraction system from the boundary level of extraction section with the forward extraction section of washing; Second part of rare earth feed liquid enters fractional extraction system from the boundary level of the rear extraction section of washing with washing section; Cleaning mixture enters fractional extraction system from last 1 grade of extraction tank. 1st grade of extraction tank balance aqueous phase is light rare earth component aqueous solution, and the light rare earth component aqueous solution of 66%～71% proceeds to rare-earth sodium saponification section, and all the other 29%～34% is light rare earth component product; Last 1 grade of extraction tank balance organic facies is the organic facies of load heavy rare earth component, all proceeds to stripping section.
5) stripping section
With the organic facies of load heavy rare earth component for treating back extraction raw material, with 4.0M～5.5M hydrochloric acid for back washing agent, countercurrent reextraction will be carried on the heavy rare earth component back extraction of organic facies to aqueous phase. Stripping section outlet organic facies is regeneration rare earth extraction organic facies, and all circulation proceeds to saponification section; Stripping section outlet raffinate aqueous phase is containing acid heavy rare earth component aqueous solution, all proceeds to extraction acid section.
6) extraction acid section
Extraction acid organic facies is kerosene or the sulfonated kerosene solution of N235 and tributyl phosphate, and the concentration of volume percent of N235 is 20%～35%, and the concentration of volume percent of tributyl phosphate is 10%～25%. Counter-current extraction removes containing the hydrochloric acid in acid heavy rare earth component aqueous solution. Extraction acid section outlet organic facies is the N235 organic facies of load hydrochloric acid and non-rare earth; Extraction acid section outlet aqueous phase is attached most importance to rare earth component aqueous solution, and the heavy rare earth component aqueous solution of 75%～79% is used as cleaning mixture, the product of all the other 21%～25% rare earth components of attaching most importance to.
7) rare-earth products
Obtain three kinds of rare-earth products: from the 1st grade of extraction tank raffinate aqueous phase of fractional extraction system, obtain the product of light rare earth component La～Nd; The enriched substance product obtaining middle rare earth component Sm～Dy the boundary level extraction tank raffinate aqueous phase of the Duan Yuhou extraction section of washing is washed from forward extraction; The product of heavy rare earth component Ho～Lu and Y is obtained from the raffinate aqueous phase of extraction acid section.
The invention have the advantages that export with existing washing section aqueous phase three～Nd/Sm～Dy/Ho～packet separating technology compared with, the present invention can be greatly lowered the acid and alkali consumption of Rare Earth Separation technical process, wherein inorganic base (organic facies saponification alkali and hydrochloric acid alkali in the anti-raffinate of neutralization) consumption can decline 58.2%～64.5%, and the consumption of hydrochloric acid (washing acid and back extraction acid) can decline 22.7%～34.2%; The wastewater discharge of rare-earth extraction separating process process significantly reduces, and the green degree of Rare Earth Separation significantly improves; Extraction tank progression can reduce 12.7%～22.2%, and the gross investment of rare-earth extraction separating process declines; Separation costs is remarkably decreased; N235 not only can extract the hydrochloric acid removed in earth solution, and can extract non-rare earth impurity, such as ferrum, lead, copper etc. in removing earth solution simultaneously, thus improving the quality of heavy rare earth product; The concentration of heavy rare earth component solution is significantly improved, and is conducive to follow-up separation process or aftertreatment technology; The treating capacity of separating technology is also improved to some extent.
Accompanying drawing explanation
Fig. 1 enters three for yttrium richness europium ore deposit two in the Nd/Sm～Dy/Ho packet separation containing slave part (saponification section, stripping section and extraction acid section) and goes out fully loaded fractional extraction architectural schematic.
In Fig. 1, HR represents acid phosphorus extractant P507. Fig. 1 does not constitute any limitation of the invention.
Detailed description of the invention
In a kind of Nd/Sm～Dy/Ho of the present invention packet being separated below in conjunction with specific embodiment, the process in yttrium richness europium ore deposit is further described.
Embodiment 1:
1) rare earth feed liquid
Yttrium richness europium ore deposit rare earth chloride solution in first part, its rare earth concentration is 1.2M, and pH value is 2; In rare earth element, the molar fraction that the molar fraction that molar fraction is 0.55, Sm～Dy is 0.15, Ho～Lu and Y of LREE La～Nd is 0.30.
Yttrium richness europium ore deposit rare earth chloride solution in second part, its rare earth concentration is 1.2M, and pH value is 1; In rare earth element, the molar fraction that the molar fraction that molar fraction is 0.55, Sm～Dy is 0.15, Ho～Lu and Y of LREE La～Nd is 0.30.
With rare earth ion molar ratio computing, the ratio of the inlet amount of first part of rare earth feed liquid and second part of rare earth feed liquid is 11.
2) rare earth extraction organic facies
Rare earth extraction organic facies is the kerosin of P507, and the concentration of volume percent of P507 is 35%; Adding fractional extraction system with light rare earth saponification organic facies form, saponification degree is 36%.
3) cleaning mixture
Cleaning mixture is the solution of heavy rare earth element (Ho～Lu and Y), and its rare earth concentration is 0.8108M, and pH value is 3.
4) fractional extraction system
Two enter three goes out fractional extraction system and is made up of 55 grades of extraction tanks, wherein extraction section 8 grades, the forward extraction section of washing 5 grades, the rear extraction section of washing 7 grades, washing section 35 grades. Light rare earth saponification organic facies enters fractional extraction system from the 1st grade of extraction tank; In first part, yttrium richness europium ore deposit rare earth feed liquid enters fractional extraction system from the 8th grade; In second part, yttrium richness europium ore deposit rare earth feed liquid enters fractional extraction system from the 20th grade; Cleaning mixture enters fractional extraction system from the 55th grade. 1st grade of extraction tank balance aqueous phase is the aqueous solution of light rare earth, and the light rare earth liquid of 66.43% proceeds to rare-earth sodium saponification section, and all the other 33.57% light rare earth liquid are product; 55th grade of extraction tank balance organic facies is the organic facies of load heavy rare earth element (Ho～Lu and Y), all proceeds to stripping section.
Other extraction process parameters are as follows: normalization extraction quantity S=2.002851, normalization washing amount W=1.522803. Second part of rare earth feed liquid inlet amount washing amount=2.002851 11 1.522803 (rare earth ion mol ratio) of first part of rare earth feed liquid inlet amount of extraction quantity. It is 0.664326 that extraction section extracts ratio, and it is 0.994039 that the forward extraction section of washing extracts ratio, and it is 0.793899 that the rear extraction section of washing extracts ratio, and it is 1.315240 that washing section extracts ratio.
5) stripping section
With the organic facies of load heavy rare earth element (Ho～Lu and Y) for treating back extraction raw material, with 4.5M hydrochloric acid for back washing agent, flow ratio O/A=19.31 1,12 stage countercurrent back extraction will be carried on the heavy rare earth element back extraction of organic facies to aqueous phase. Stripping section outlet organic facies is regeneration P507 organic facies, and all circulation proceeds to saponification section; Stripping section outlet raffinate aqueous phase is the heavy rare-earth solution containing 2.068M hydrochloric acid, and heavy rare earth concentration is 0.8107M, all proceeds to extraction acid section.
6) extraction acid section
Extraction acid organic facies is the kerosin of N235 and tributyl phosphate, and the concentration of volume percent of N235 is 25%, and the concentration of volume percent of tributyl phosphate is 15%. Flow ratio O/A=6 Isosorbide-5-Nitrae stage countercurrent extracts the hydrochloric acid removed containing in the heavy rare-earth solution of 2.068M hydrochloric acid. Extraction acid section outlet organic facies is the N235 organic facies of load hydrochloric acid and non-rare earth; Extraction acid section outlet aqueous phase is 0.8107M heavy rare-earth solution, and its pH value is 3; 76.03% heavy rare-earth solution is used as rare earth two and enters three cleaning mixture going out fractional extraction, and all the other 23.97% heavy rare-earth solutions are product.
7) rare-earth products
Obtaining light rare earth (La～Nd) product from the 1st grade of extraction tank raffinate aqueous phase of fractional extraction system, its relative purity is 99.99%, and yield is 92.00%;Obtaining middle rare earth Sm～Dy enriched substance product from the 14th grade of extraction tank raffinate aqueous phase of fractional extraction system, wherein rare-earth Sm～Dy relative purity is 59.05%, and yield is 99.98%; Obtaining the product of heavy rare earth (Ho～Lu and Y) from the raffinate aqueous phase of extraction acid section, its relative purity is 99.99%, and yield is 80.00%.
8) separating effect contrast
Enter with existing two three go out rare-earth fractionation extraction process compared with, the consumption of the inorganic base of the present invention (organic facies saponification alkali and neutralize hydrochloric acid alkali in anti-raffinate) declines 64.43%; The consumption of hydrochloric acid (washing acid and back extraction acid) declines 34.19%; Extraction tank progression reduces 8 grades, declines 12.70%.
Embodiment 2:
1) rare earth feed liquid
Yttrium richness europium ore deposit rare earth chloride solution in first part, its rare earth concentration is 1.0M, and pH value is 3; In rare earth element, the molar fraction that the molar fraction that molar fraction is 0.55, Sm～Dy is 0.15, Ho～Lu and Y of LREE La～Nd is 0.30.
Yttrium richness europium ore deposit rare earth chloride solution in second part, its rare earth concentration is 1.0M, and pH value is 1; In rare earth element, the molar fraction that the molar fraction that molar fraction is 0.55, Sm～Dy is 0.15, Ho～Lu and Y of LREE La～Nd is 0.30.
With rare earth ion molar ratio computing, the ratio of the inlet amount of first part of rare earth feed liquid and second part of rare earth feed liquid is 21.
2) rare earth extraction organic facies
Rare earth extraction organic facies is the kerosin of P507, and the concentration of volume percent of P507 is 36%; Adding fractional extraction system with light rare earth saponification organic facies form, saponification degree is 35%.
3) cleaning mixture
Cleaning mixture is the solution of heavy rare earth element (Ho～Lu and Y), and its rare earth concentration is 0.9009M, and pH value is 2.
4) fractional extraction system
Two enter three goes out fractional extraction system and is made up of 49 grades of extraction tanks, wherein extraction section 8 grades, the forward extraction section of washing 5 grades, the rear extraction section of washing 4 grades, washing section 32 grades. Light rare earth saponification organic facies enters fractional extraction system from the 1st grade of extraction tank; In first part, yttrium richness europium ore deposit rare earth feed liquid enters fractional extraction system from the 8th grade; In second part, yttrium richness europium ore deposit rare earth feed liquid enters fractional extraction system from the 17th grade; Cleaning mixture enters fractional extraction system from the 49th grade of extraction tank. 1st grade of extraction tank balance aqueous phase is the aqueous solution of light rare earth, and the light rare earth liquid of 69.64% proceeds to rare-earth sodium saponification section, and all the other 30.36% light rare earth liquid are product; 49th grade of extraction tank balance organic facies is the organic facies of load heavy rare earth element, all proceeds to stripping section.
Other extraction process parameters are as follows: normalization extraction quantity S=3.482785, normalization washing amount W=2.762713. Second part of rare earth feed liquid inlet amount washing amount=3.482785 21 2.762713 (rare earth ion mol ratio) of first part of rare earth feed liquid inlet amount of extraction quantity. It is 0.696446 that extraction section extracts ratio, and it is 1.160619 that the forward extraction section of washing extracts ratio, and it is 0.925605 that the rear extraction section of washing extracts ratio, and it is 1.260639 that washing section extracts ratio.
5) stripping section
With the organic facies of load heavy rare earth element (Ho～Lu and Y) for treating back extraction raw material, with 5.0M hydrochloric acid for back washing agent, flow ratio O/A=21.45 1,12 stage countercurrent back extraction will be carried on the heavy rare earth element back extraction of organic facies to aqueous phase. Stripping section outlet organic facies is regeneration P507 organic facies, and all circulation proceeds to saponification section; Stripping section outlet raffinate aqueous phase is the heavy rare-earth solution containing 2.297M hydrochloric acid, and heavy rare earth concentration is 0.9008M, all proceeds to extraction acid section.
6) extraction acid section
Extraction acid organic facies is the kerosin of N235 and tributyl phosphate, and the concentration of volume percent of N235 is 30%, and the concentration of volume percent of tributyl phosphate is 20%. Flow ratio O/A=6 1,5 stage countercurrent extracts the hydrochloric acid removed containing in the heavy rare-earth solution of 2.297M hydrochloric acid. Extraction acid section outlet organic facies is the N235 organic facies of load hydrochloric acid and non-rare earth; Extraction acid section outlet aqueous phase is 0.9008M heavy rare-earth solution, and its pH value is 2; 79.32% heavy rare-earth solution is used as rare earth two and enters three cleaning mixture going out fractional extraction, and all the other 20.68% heavy rare-earth solutions are product.
7) rare-earth products
Obtaining light rare earth (La～Nd) product from the 1st grade of extraction tank raffinate aqueous phase of fractional extraction system, its relative purity is 99.99%, and yield is 92.00%; Obtaining middle rare earth Sm～Dy enriched substance product from the 14th grade of extraction tank raffinate aqueous phase of fractional extraction system, wherein rare-earth Sm～Dy relative purity is 59.05%, and yield is 99.98%; Obtaining the product of heavy rare earth (Ho～Lu and Y) from the raffinate aqueous phase of extraction acid section, its relative purity is 99.99%, and yield is 80.00%.
8) separating effect contrast
Enter with existing two three go out rare-earth fractionation extraction process compared with, the consumption of the inorganic base of the present invention (organic facies saponification alkali and neutralize hydrochloric acid alkali in anti-raffinate) declines 58.76%; The consumption of hydrochloric acid (washing acid and back extraction acid) declines 23.70%; Extraction tank progression reduces 14 grades, declines 22.22%.
Embodiment 3:
1) rare earth feed liquid
Yttrium richness europium ore deposit rare earth chloride solution in first part, its rare earth concentration is 1.5M, and pH value is 2; In rare earth element, the molar fraction that the molar fraction that molar fraction is 0.55, Sm～Dy is 0.15, Ho～Lu and Y of LREE La～Nd is 0.30.
Yttrium richness europium ore deposit rare earth chloride solution in second part, its rare earth concentration is 1.0M, and pH value is 1; In rare earth element, the molar fraction that the molar fraction that molar fraction is 0.50, Sm～Dy is 0.15, Ho～Lu and Y of LREE La～Nd is 0.35.
With rare earth ion molar ratio computing, the ratio of the inlet amount of first part of rare earth feed liquid and second part of rare earth feed liquid is 11.
2) rare earth extraction organic facies
Rare earth extraction organic facies is the sulfonated kerosene solution of P507, and the concentration of volume percent of P507 is 30%; Adding fractional extraction system with light rare earth saponification organic facies form, saponification degree is 40%.
3) cleaning mixture
Cleaning mixture is the solution of heavy rare earth element (Ho～Lu and Y), and its rare earth concentration is 0.7207M, and pH value is 4.
4) fractional extraction system
Two enter three goes out fractional extraction system and is made up of 55 grades of extraction tanks, wherein extraction section 8 grades, the forward extraction section of washing 5 grades, the rear extraction section of washing 7 grades, washing section 35 grades. Light rare earth saponification organic facies enters fractional extraction system from the 1st grade of extraction tank; In first part, yttrium richness europium ore deposit rare earth feed liquid enters fractional extraction system from the 8th grade; In second part, yttrium richness europium ore deposit rare earth feed liquid enters fractional extraction system from the 20th grade; Cleaning mixture enters fractional extraction system from the 55th grade of extraction tank. 1st grade of extraction tank balance aqueous phase is the aqueous solution of light rare earth, and the light rare earth liquid of 68.46% proceeds to rare-earth sodium saponification section, and all the other 31.54% light rare earth liquid are product; 55th grade of extraction tank balance organic facies is the organic facies of load heavy rare earth element, all proceeds to stripping section.
Other extraction process parameters are as follows: normalization extraction quantity S=2.096508, normalization washing amount W=1.576456.Second part of rare earth feed liquid inlet amount washing amount=2.096508 11 1.576456 (rare earth ion mol ratio) of first part of rare earth feed liquid inlet amount of extraction quantity. It is 0.684570 that extraction section extracts ratio, and it is 1.016480 that the forward extraction section of washing extracts ratio, and it is 0.813718 that the rear extraction section of washing extracts ratio, and it is 1.329887 that washing section extracts ratio.
5) stripping section
With the organic facies of load heavy rare earth element for treating back extraction raw material, with 4.0M hydrochloric acid for back washing agent, flow ratio O/A=18.02 1,12 stage countercurrent back extraction will be carried on the heavy rare earth element back extraction of organic facies to aqueous phase. Stripping section outlet organic facies is regeneration P507 organic facies, and all circulation proceeds to saponification section; Stripping section outlet raffinate aqueous phase is the heavy rare-earth solution containing 1.834M hydrochloric acid, and heavy rare earth concentration is 0.7206M, all proceeds to extraction acid section.
6) extraction acid section
Extraction acid organic facies is the sulfonated kerosene solution of N235 and tributyl phosphate, and the concentration of volume percent of N235 is 20%, and the concentration of volume percent of tributyl phosphate is 10%. Flow ratio O/A=7 1,3 stage countercurrent extracts the hydrochloric acid removed containing in the heavy rare-earth solution of 1.834M hydrochloric acid. Extraction acid section outlet organic facies is the N235 organic facies of load hydrochloric acid and non-rare earth; Extraction acid section outlet aqueous phase is 0.7206M heavy rare-earth solution, and its pH value is 4; 75.19% heavy rare-earth solution is used as rare earth two and enters three cleaning mixture going out fractional extraction, and all the other 24.81% heavy rare-earth solutions are product.
7) rare-earth products
Obtaining light rare earth (La～Nd) product from the 1st grade of extraction tank raffinate aqueous phase of fractional extraction system, its relative purity is 99.99%, and yield is 92.00%; Obtaining middle rare earth Sm～Dy enriched substance product from the 14th grade of extraction tank raffinate aqueous phase of fractional extraction system, wherein rare-earth Sm～Dy relative purity is 58.36%, and yield is 99.98%; Obtaining the product of heavy rare earth (Ho～Lu and Y) from the raffinate aqueous phase of extraction acid section, its relative purity is 99.99%, and yield is 80.00%.
8) separating effect contrast
Enter with existing two three go out rare-earth fractionation extraction process compared with, the consumption of the inorganic base of the present invention (organic facies saponification alkali and neutralize hydrochloric acid alkali in anti-raffinate) declines 63.72%; The consumption of hydrochloric acid (washing acid and back extraction acid) declines 32.89%; Extraction tank progression reduces 11 grades, declines 16.67%.
Embodiment 4:
1) rare earth feed liquid
Yttrium richness europium ore deposit rare earth chloride solution in first part, its rare earth concentration is 1.0M, and pH value is 3; In rare earth element, the molar fraction that the molar fraction that molar fraction is 0.55, Sm～Dy is 0.15, Ho～Lu and Y of LREE La～Nd is 0.30.
Yttrium richness europium ore deposit rare earth chloride solution in second part, its rare earth concentration is 1.5M, and pH value is 2; In rare earth element, the molar fraction that the molar fraction that molar fraction is 0.50, Sm～Dy is 0.15, Ho～Lu and Y of LREE La～Nd is 0.35.
With rare earth ion molar ratio computing, the ratio of the inlet amount of first part of rare earth feed liquid and second part of rare earth feed liquid is 21.
2) rare earth extraction organic facies
Rare earth extraction organic facies is the kerosin of P507, and the concentration of volume percent of P507 is 45%; Adding fractional extraction system with light rare earth saponification organic facies form, saponification degree is 30%.
3) cleaning mixture
Cleaning mixture is the solution of heavy rare earth element (Ho～Lu and Y), and its rare earth concentration is 0.9910M, and pH value is 1.
4) fractional extraction system
Two enter three goes out fractional extraction system and is made up of 52 grades of extraction tanks, wherein extraction section 8 grades, the forward extraction section of washing 5 grades, the rear extraction section of washing 8 grades, washing section 31 grades.Light rare earth saponification organic facies enters fractional extraction system from the 1st grade of extraction tank; In first part, yttrium richness europium ore deposit rare earth feed liquid enters fractional extraction system from the 8th grade; In second part, yttrium richness europium ore deposit rare earth feed liquid enters fractional extraction system from the 21st grade; Cleaning mixture enters fractional extraction system from the 52nd grade of extraction tank. 1st grade of extraction tank balance aqueous phase is the aqueous solution of light rare earth, and the light rare earth liquid of 70.91% proceeds to rare-earth sodium saponification section, and all the other 29.09% light rare earth liquid are product; 52nd grade of extraction tank balance organic facies is load heavy rare earth element organic facies, all proceeds to stripping section.
Other extraction process parameters are as follows: normalization extraction quantity S=3.587702, normalization washing amount W=2.827626. Second part of rare earth feed liquid inlet amount washing amount=3.587702 21 2.827626 (rare earth ion mol ratio) of first part of rare earth feed liquid inlet amount of extraction quantity. It is 0.709072 that extraction section extracts ratio, and it is 1.172560 that the forward extraction section of washing extracts ratio, and it is 0.937318 that the rear extraction section of washing extracts ratio, and it is 1.268804 that washing section extracts ratio.
5) stripping section
With the organic facies of load heavy rare earth element for treating back extraction raw material, with 5.5M hydrochloric acid for back washing agent, flow ratio O/A=22.02 1,6 stage countercurrent back extraction will be carried on the heavy rare earth element back extraction of organic facies to aqueous phase. Stripping section outlet organic facies is regeneration P507 organic facies, and all circulation proceeds to saponification section; Stripping section outlet raffinate aqueous phase is the heavy rare-earth solution containing 2.527M hydrochloric acid, and heavy rare earth concentration is 0.9909M, all proceeds to extraction acid section.
6) extraction acid section
Extraction acid organic facies is the kerosin of N235 and tributyl phosphate, and the concentration of volume percent of N235 is 35%, and the concentration of volume percent of tributyl phosphate is 25%. Flow ratio O/A=6 1,6 stage countercurrent extracts the hydrochloric acid removed containing in the heavy rare-earth solution of 2.527M hydrochloric acid. Extraction acid section outlet organic facies is the N235 organic facies of load hydrochloric acid and non-rare earth; Extraction acid section outlet aqueous phase is 0.9909M heavy rare-earth solution, and its pH value is 1; 78.81% heavy rare-earth solution is used as rare earth two and enters three cleaning mixture going out fractional extraction, and all the other 21.19% heavy rare-earth solutions are product.
7) rare-earth products
Obtaining light rare earth (La～Nd) product from the 1st grade of extraction tank raffinate aqueous phase of fractional extraction system, its relative purity is 99.99%, and yield is 92.00%; Obtaining middle rare earth Sm～Dy enriched substance product from the 14th grade of extraction tank raffinate aqueous phase of fractional extraction system, wherein rare-earth Sm～Dy relative purity is 58.59%, and yield is 99.98%; Obtaining the product of heavy rare earth (Ho～Lu and Y) from the raffinate aqueous phase of extraction acid section, its relative purity is 99.99%, and yield is 80.00%.
8) separating effect contrast
Enter with existing two three go out rare-earth fractionation extraction process compared with, the consumption of the inorganic base of the present invention (organic facies saponification alkali and neutralize hydrochloric acid alkali in anti-raffinate) declines 58.25%; The consumption of hydrochloric acid (washing acid and back extraction acid) declines 22.77%; Extraction tank progression reduces 13 grades, declines 20.00%.
Claims (1)
1. the process in yttrium richness europium ore deposit in Nd/Sm～Dy/Ho packet separation, it is characterized in that: with the rare earth chloride solution in middle yttrium richness europium ore deposit for feed liquid, the extraction section of the washing aqueous phase of fractional extraction system is located in 3rd outlet, is provided with the N235 extraction acid section for extracting acid agent, tributyl phosphate TBP is demulsifier between washing section and stripping section; Utilize the extraction acid effect of N235 to enter three with yttrium richness europium ore deposit two in realizing to go out fractional extraction system middle rare earth extraction quantity and be not less than rare-earth sodium saponification amount;
Process program is as follows:
1) rare earth feed liquid
With the rare earth chloride solution in middle yttrium richness europium ore deposit for feed liquid, rare earth feed liquid middle rare earth concentration is 1.0M～1.5M, and pH value is 1～3; Middle yttrium richness europium ore deposit rare earth feed liquid is divided into two parts; In rare earth element, the light rare earth molar fraction in first part of rare earth feed liquid is not less than the light rare earth molar fraction in second part, and namely the middle heavy rare earth molar fraction in second part of rare earth feed liquid is not less than the middle heavy rare earth molar fraction in first part;
2) rare earth extraction organic facies
Rare earth extraction organic facies is kerosene or the sulfonated kerosene solution of P507, and the concentration of volume percent of P507 is 30%～45%; Adding fractional extraction system with light rare earth La～Nd saponification organic facies form, saponification degree is 30%～40%;
3) cleaning mixture
Cleaning mixture is the solution of heavy rare earth element Ho～Lu and Y, and its rare earth concentration is 0.72M～0.99M, and pH value is 1～4;
4) fractional extraction system
Fractional extraction system is two enter three and go out fractional extraction system, is made up of extraction section, the extraction section of washing and washing section, and the extraction section of washing aqueous phase is located in the 3rd outlet, and the extraction section of washing is divided into the forward extraction section of washing and the rear extraction section of washing by the 3rd outlet; Light rare earth saponification organic facies enters fractional extraction system from the 1st grade of extraction tank; First part of rare earth feed liquid enters fractional extraction system from the boundary level of extraction section with the forward extraction section of washing; Second part of rare earth feed liquid enters fractional extraction system from the boundary level of the rear extraction section of washing with washing section; Cleaning mixture enters fractional extraction system from last 1 grade of extraction tank; 1st grade of extraction tank balance aqueous phase is light rare earth component aqueous solution, and the light rare earth component aqueous solution of 66%～71% proceeds to rare-earth sodium saponification section, and all the other 29%～34% is light rare earth component product; Last 1 grade of extraction tank balance organic facies is the organic facies of load heavy rare earth component, all proceeds to stripping section;
5) stripping section
With the organic facies of load heavy rare earth component for treating back extraction raw material, with 4.0M～5.5M hydrochloric acid for back washing agent, countercurrent reextraction will be carried on the heavy rare earth component back extraction of organic facies to aqueous phase; Stripping section outlet organic facies is regeneration rare earth extraction organic facies, and all circulation proceeds to saponification section; Stripping section outlet raffinate aqueous phase is containing acid heavy rare earth component aqueous solution, all proceeds to extraction acid section;
6) extraction acid section
Extraction acid organic facies is kerosene or the sulfonated kerosene solution of N235 and tributyl phosphate, and the concentration of volume percent of N235 is 20%～35%, and the concentration of volume percent of tributyl phosphate is 10%～25%; Counter-current extraction removes containing the hydrochloric acid in acid heavy rare earth component aqueous solution; Extraction acid section outlet organic facies is the N235 organic facies of load hydrochloric acid and non-rare earth; Extraction acid section outlet aqueous phase is attached most importance to rare earth component aqueous solution, and the heavy rare earth component aqueous solution of 75%～79% is used as cleaning mixture, the product of all the other 21%～25% rare earth components of attaching most importance to;
7) rare-earth products
Obtain three kinds of rare-earth products: from the 1st grade of extraction tank raffinate aqueous phase of fractional extraction system, obtain the product of light rare earth component La～Nd; The enriched substance product obtaining middle rare earth component Sm～Dy the boundary level extraction tank raffinate aqueous phase of the Duan Yuhou extraction section of washing is washed from forward extraction; The product of heavy rare earth component Ho～Lu and Y is obtained from the raffinate aqueous phase of extraction acid section.
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| CN105803229B (en) * | 2016-05-19 | 2017-11-14 | 南昌航空大学 | A kind of extraction and separation technology for directly preparing 5N level europiums |
| CN106498191B (en) * | 2016-12-05 | 2018-06-01 | 南昌航空大学 | The method of three feed inlet fractional extraction separation of mixed rare-earth |
| CN106498193B (en) * | 2016-12-22 | 2019-07-26 | 南昌航空大学 | A kind of extracting process of three kinds of rare earths materials of grouping separation |
| CN109097606B (en) * | 2018-08-16 | 2020-07-28 | 南昌航空大学 | Separation process for co-producing pure dysprosium and pure thulium by fractional extraction |
| CN108950253B (en) * | 2018-08-20 | 2020-07-28 | 南昌航空大学 | Separation method for co-production of pure neodymium and pure lutetium by fractional extraction |
| CN111074070B (en) * | 2020-01-20 | 2021-06-29 | 广东省稀有金属研究所 | Method for extracting yttrium from marine rare earth sulfuric acid leaching solution and extracted organic phase |
| CN114892002A (en) * | 2022-05-29 | 2022-08-12 | 江西农业大学 | Extraction and separation process for heavy rare earth TmYbLu concentrate |
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