CN109913649B - Loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore - Google Patents

Loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore Download PDF

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CN109913649B
CN109913649B CN201910331004.0A CN201910331004A CN109913649B CN 109913649 B CN109913649 B CN 109913649B CN 201910331004 A CN201910331004 A CN 201910331004A CN 109913649 B CN109913649 B CN 109913649B
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rare earth
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钟盛华
何钦
李彩毅
杨冯杰
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Jiangxi Agricultural University
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Abstract

A five-outlet extraction process for pre-separating loaded organic phase of light rare earth ore belongs to the technology of extracting and separating rare earth by solvent. Pre-separating and extracting, namely pre-washing an outlet organic phase (loaded with Sm-LuY and a small amount of La-Nd rare earth) of the light rare earth ore pre-separating and extracting, and then flowing into a five-outlet extraction and separation process of La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY. In the five-outlet process, pure Sm product can be obtained at low cost, an organic phase at an outlet of a pre-dividing washing front section of the novel pre-dividing washing process is divided into two parts, and one part of the organic phase flows into a pre-dividing washing rear section. Another portion of the organic phase flows into a five outlet process. The grade of the middle outlet of the five-outlet extraction separation process is improved, the processing capacity is increased, and the storage tank amount of the extracting agent and the rare earth metal is reduced. The novel process has the advantages of reduced acid and alkali consumption, reduced production cost, reduced industrial discharge, environmental friendliness and advanced extraction and separation process.

Description

Loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore
Technical Field
The invention relates to a loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore, belonging to the field of rare earth hydrometallurgy. More particularly, the method belongs to the technology of rare earth extraction separation by solvent.
Background
Rare earth is an indispensable strategic resource for transforming the traditional industry, developing high and new technology and national defense advanced technology in all countries in the world at present. The rare earth elements are widely applied to the fields of luminescent materials, magnetic materials, metallurgy, ceramics, electronic communication, petrochemical industry and various functional materials. China is a world large country of rare earth resources, and has large light rare earth ores and rare ion adsorption rare earth ore resources in the world. The light rare earth ore resources in China are rich, and mainly comprise: baobaibo mainly uses bastnaesite, accompanied by partial monazite (which can be called as the first rare earth ore in the world); hamartite of tetrachinum; bastnaesite from microthan, Shandong; monazite mine of the southern Shanhai province; southern ionic light rare earth ore and the like.
Solvent extraction is the main means for separating and purifying rare earth in rare earth industrial production. The research work of solvent extraction separation of rare earth in China is internationally leading to the development of a plurality of advanced rare earth separation process technologies. The 'pre-separation yield-increasing extraction' (92106000.9) of professor Zhongshenghua firstly discloses a separation method of pre-separation extraction, and the multi-component raw materials of rare earth elements are firstly separated by a pre-separation process (countercurrent extraction and/or countercurrent washing), so that the direct feeding amount can be reduced, and the raw materials can enter fractional extraction from two or more feeding holes after the pre-separation extraction, thereby improving the processing capacity of the process and reducing the usage amount of an extractant organic phase, and further reducing the acid-base consumption and the waste water discharge. The high efficiency, low consumption and green production of the rare earth separation process are always desired by industrial and mining enterprises and society, and are also the targets of continuous research and pursuit. In extraction systems using more extracting agents P507, P204 and the like in industry, the separation coefficient of Nd/Sm is larger, light rare earth ore is pre-extracted by a pre-extraction method, and Sm-LuY and a small amount of La-Nd rare earth are loaded on an outlet organic phase. For the separation of the organic phase loaded with rare earth at the outlet, the invention researches and forms a new process for pre-dividing and washing five outlets of La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY. The pure Sm product can be obtained at lower cost in the process, and due to the novel pre-dividing and washing process, the processing capacity of the extraction and separation process is improved, the storage tank amount of an extracting agent and rare earth metal is reduced, the consumption of acid-base chemical raw materials is reduced, the production cost is reduced, and the industrial discharge is reduced, thereby being beneficial to environmental protection. The process is a more advanced process flow.
Disclosure of Invention
The invention provides a loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore, which adopts a pre-separation extraction method to pre-wash an outlet organic phase (loaded with Sm-LuY and a small amount of La-Nd rare earth) of the pre-separation extraction of the light rare earth ore and then flow into a La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet extraction separation process. The pure Sm product can be obtained at low cost in the five-outlet process, and the new pre-separation washing process improves the grade of the middle outlet of the five-outlet extraction separation process, increases the processing capacity, reduces the storage tank amount of the extracting agent and the rare earth metal, and is a more advanced separation process.
The technical scheme of the invention is as follows: a loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore is characterized in that: an outlet organic phase loaded Sm-LuY of the light rare earth ore subjected to pre-separation countercurrent extraction and a small amount of La-Nd rare earth as organic materials enter a pre-separation washing process, an outlet water phase and an outlet organic phase after pre-separation washing enter a La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process, and the five-outlet process obtains a pure Sm product and four components of La-Nd, SmEuGd, GdTbDy and Ho-LuY; the specific technical scheme is as follows: the pre-dividing and washing process consists of a pre-dividing and washing front section and a pre-dividing and washing rear section, and is characterized in that part of an outlet organic phase of the pre-dividing and washing front section flows into the five-outlet process from a position between a SmEuGd outlet and a GdTbDy outlet of the five-outlet process; or the pre-dividing washing process consists of a pre-dividing washing front section and a pre-dividing washing rear section, and is characterized in that part of outlet organic phase of the pre-dividing washing front section flows into the five-outlet process from a pure Sm outlet and a SmEuGd outlet of the five-outlet process; or the outlet organic phase of the pre-separation washing section flows into the five-outlet process from the position between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process; these three embodiments are as follows.
Scheme 1: the organic phase at the outlet of the pre-separation washing front section part flows in from the position between SmEuGd and GdTbDy outlets of the five outlets.
The pre-separation washing section of the embodiment 1 is a countercurrent washing process and comprises a pre-separation washing front section and a pre-separation washing rear section, and is characterized in that part of an outlet organic phase of the pre-separation washing front section flows into a five-outlet process from a position between a SmEuGd outlet and a GdTbDy outlet of the five-outlet process, and the technical scheme comprises the steps.
(1) After the light rare earth ore is subjected to pre-divided countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth are taken as organic materials to flow into the 1 st stage of the pre-divided washing front section and an outlet aqueous phase from the pre-divided washing rear section for countercurrent washing.
(2) Part of the organic phase at the outlet of the pre-separation washing front section flows into the pre-separation washing rear section and is washed by the washing acid flowing in from the last stage, namely the nth stage, of the pre-separation washing rear section in a countercurrent mode, and the water phase at the outlet of the pre-separation washing rear section flows into the last stage of the pre-separation washing front section.
(3) The water phase at the 1 st stage outlet of the pre-separating and washing front stage flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, the other part of the organic phase at the outlet of the pre-separating and washing front stage flows into the five-outlet process from the position between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process, and the organic phase at the n th stage outlet of the pre-separating and washing rear stage flows into the five-outlet process from the position between the organic phase at the last outlet of the five-; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, the Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99.5%, and the SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet.
Scheme 2: part of the outlet organic phase at the front-stage of the pre-separation washing flows in from the part between pure Sm and GdTbDy outlets of the five outlets.
The pre-divided washing section of the embodiment 2 is a countercurrent washing process which comprises a pre-divided washing front section and a pre-divided washing rear section, and is characterized in that part of an outlet organic phase of the pre-divided washing front section flows into a five-outlet process from a position between a pure Sm outlet and a SmEuGd outlet of the five-outlet process, and the technical scheme comprises the steps.
(1) After the light rare earth ore is subjected to pre-divided countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth are taken as organic materials to flow into the 1 st stage of the pre-divided washing front section and an outlet aqueous phase from the pre-divided washing rear section for countercurrent washing.
(2) Part of the organic phase at the outlet of the pre-separation washing front section flows into the pre-separation washing rear section and is washed by the washing acid flowing in from the last stage, namely the nth stage, of the pre-separation washing rear section in a countercurrent mode, and the water phase at the outlet of the pre-separation washing rear section flows into the last stage of the pre-separation washing front section.
(3) The water phase at the 1 st stage outlet of the pre-separation washing front stage flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, the other part of the organic phase at the outlet of the pre-separation washing front stage flows into the five-outlet process from the position between the pure Sm outlet and the SmEuGd outlet of the five-outlet process, and the organic phase at the n th stage outlet of the pre-separation washing rear stage flows into the five-outlet process from the position between the organic phase at the last outlet of the five-outlet process and the G; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, the Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99.5%, and the SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet.
Scheme 3: the outlet organic phase of the pre-split wash stage flowed in between the five outlet process SmEuGd and GdTbDy outlets.
The pre-fractionation washing stage of this embodiment 3 is a counter current washing process, the technical solution of which comprises the steps.
(1) After the light rare earth ore is subjected to pre-separation countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth serving as organic materials flow into the washing acid entering the 1 st stage and the nth stage of the pre-separation washing section for countercurrent washing.
(2) The water phase at the 1 st stage outlet of the pre-separation washing section flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, and the organic phase at the outlet of the pre-separation washing section flows into the five-outlet process from the position between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99%, and SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet.
The light rare earth ore of the invention comprises: bastnaesite, monazite, cerium niobium perovskite, southern ion light rare earth ore, one of these ores, or a combination of these ores; the light rare earth ore is produced by Baotou, Sichuan crown Ning, Shandong Weishan, Guandong south mountain sea or other areas.
The pre-dividing and washing process and the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process are a hydrochloric acid system, a nitric acid system or a sulfuric acid system.
The Sm-LuY and a small amount of La-Nd rare earth are loaded on the outlet organic phase of the light rare earth ore subjected to pre-divided countercurrent extraction, and the content of La-Nd rare earth in the loaded rare earth is greatly reduced compared with that in the light rare earth ore.
The organic phase at the outlet of the pre-dividing washing front section is divided into two parts, wherein one part of the organic phase flows into the pre-dividing washing rear section, and the other part of the organic phase flows into a five-outlet process of La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY; the two organic phases must be controlled in their flow rate, or at least in one of them.
The organic phase consists of an extracting agent and a diluting agent, wherein the extracting agent is 2-ethylhexyl mono-2-ethylhexyl phosphate (also called HEH [ EHP ], or P507), or di (2-ethylhexyl) phosphoric acid (also called HDEHP, or P204), or other extracting agents, and the concentration of the extracting agent in the organic phase is 0.8-1.6 mol.L < -1 >; the diluent is kerosene or n-hexane organic solvent.
The method is characterized in that Sm-LuY loaded on an outlet organic phase of light rare earth ore subjected to pre-separation countercurrent extraction and a small amount of La-Nd rare earth are fed into a pre-separation washing process as an organic material, and an outlet water phase and an outlet organic phase after pre-separation washing enter a La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process, wherein the pre-separation washing process forms include but are not limited to the pre-separation washing processes of embodiment 1, embodiment 2 and embodiment 3 of the invention.
The technical scheme of the invention has the advantages that: pre-separating and extracting, namely pre-washing an outlet organic phase (loaded with Sm-LuY and a small amount of La-Nd rare earth) of the light rare earth ore pre-separating and extracting, and then flowing into a five-outlet extraction and separation process of La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY. Pure Sm product can be obtained at low cost in the five-outlet process. The organic phase at the outlet of the pre-divided washing front section of the new pre-divided washing process embodiment 1 and embodiment 2 is divided into two parts, and one part of the organic phase flows into the pre-divided washing rear section. The other part of the organic phase flows into a five-outlet process of La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY. The grade of the middle outlet of the five-outlet extraction separation process is improved, the processing capacity is increased, and the storage tank amount of the extracting agent and the rare earth metal is reduced. The consumption of acid-base chemical raw materials of the new process is reduced, the production cost is reduced, the industrial emission is reduced, the green environmental protection is facilitated, and the new process is a more advanced extraction separation process flow.
Drawings
The attached drawing is a schematic diagram of a loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore. It is to be understood, however, that the drawings are designed solely for purposes of illustration and not as a definition of the limits of the invention, for which reference should be made to the appended claims.
FIG. 1 is a schematic process flow diagram of embodiment 1 of the present invention. FIG. 2 is a schematic process flow diagram of embodiment 2 of the present invention. FIG. 3 is a schematic process flow diagram of embodiment 3 of the present invention. In fig. 1, 2 and 3, the letters of the inflow process are represented as: s is an alkali saponification organic phase, W is a washing acid, and H is a stripping acid.
FIG. 4 is a schematic of the preparation of an alkali saponified organic phase. In the figure, S is an alkali saponification organic phase.
Detailed Description
The invention relates to a loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore, which combines the attached drawing, and three embodiments of the process are as follows.
Embodiment 1, referring to fig. 1, the pre-washing section is a countercurrent washing process comprising a pre-washing front section and a pre-washing rear section, and is characterized in that part of the outlet organic phase of the pre-washing front section flows into the five-outlet process from the space between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process, and the technical scheme comprises the steps of: (1) after the light rare earth ore is subjected to pre-divided countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth are taken as organic materials to flow into the 1 st stage of the pre-divided washing front section and an outlet aqueous phase from the pre-divided washing rear section for countercurrent washing. (2) Part of the organic phase at the outlet of the pre-separation washing front section flows into the pre-separation washing rear section and is washed by the washing acid flowing in from the last stage, namely the nth stage, of the pre-separation washing rear section in a countercurrent mode, and the water phase at the outlet of the pre-separation washing rear section flows into the last stage of the pre-separation washing front section. (3) The water phase at the 1 st stage outlet of the pre-separating and washing front stage flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, the other part of the organic phase at the outlet of the pre-separating and washing front stage flows into the five-outlet process from the position between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process, and the organic phase at the n th stage outlet of the pre-separating and washing rear stage flows into the five-outlet process from the position between the organic phase at the last outlet of the five-; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, the Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99.5%, and the SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet.
Embodiment 2, referring to fig. 2, the pre-washing stage is a countercurrent washing process comprising a pre-washing front stage and a pre-washing rear stage, and is characterized in that part of the outlet organic phase of the pre-washing front stage flows into the five-outlet process from a pure Sm outlet and a smegd outlet of the five-outlet process, and the technical scheme comprises the following steps: (1) after the light rare earth ore is subjected to pre-divided countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth are taken as organic materials to flow into the 1 st stage of the pre-divided washing front section and an outlet aqueous phase from the pre-divided washing rear section for countercurrent washing. (2) Part of the organic phase at the outlet of the pre-separation washing front section flows into the pre-separation washing rear section and is washed by the washing acid flowing in from the last stage, namely the nth stage, of the pre-separation washing rear section in a countercurrent mode, and the water phase at the outlet of the pre-separation washing rear section flows into the last stage of the pre-separation washing front section. (3) The water phase at the 1 st stage outlet of the pre-separation washing front stage flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, the other part of the organic phase at the outlet of the pre-separation washing front stage flows into the five-outlet process from the position between the pure Sm outlet and the SmEuGd outlet of the five-outlet process, and the organic phase at the n th stage outlet of the pre-separation washing rear stage flows into the five-outlet process from the position between the organic phase at the last outlet of the five-outlet process and the G; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, the Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99.5%, and the SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet.
Embodiment 3, referring to fig. 3, the pre-fractionation washing section is a counter-current washing process, the technical scheme of which comprises the steps of: (1) after the light rare earth ore is subjected to pre-separation countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth serving as organic materials flow into the washing acid entering the 1 st stage and the nth stage of the pre-separation washing section for countercurrent washing. (2) The water phase at the 1 st stage outlet of the pre-separation washing section flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, and the organic phase at the outlet of the pre-separation washing section flows into the five-outlet process from the position between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99%, and SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet.
The following examples are given by way of illustration of the present invention and are not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Example 1.
The light rare earth ore is prepared from Sichuan bastnaesite through dissolving, purifying and proportioning, and the rare earth concentration of the chlorinated rare earth solution is 1.6 mol.L-1And the pH value is ﹦ 2-3, and the rare earth is distributed as follows:
Figure 964581DEST_PATH_IMAGE001
。
the organic phase is extracted by an extractant P507(2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester) and a diluent kerosene, P in the organic phase507The concentration is 1.5 mol.L-1，P507The saponification concentration was 0.56 mol. L-1. The loaded organic phase pre-separation five-outlet extraction process of the invention is adopted as the embodiment 1, the process flow schematic diagram of the process is shown in the attached figure 1, and the process is implemented according to the specific technical scheme steps of the embodiment 1.
Through the embodiment 1 of the five-outlet extraction process for pre-separating the loaded organic phase of the light rare earth ore, 99 percent of pure Sm product and four enrichments of La-Nd, SmEuGd, GdTbDy and Ho-LuY can be obtained after extraction and separation.
Through measurement and calculation, compared with the traditional extraction separation process, the extraction separation effect of the embodiment 1 of the loaded organic phase pre-separation five-outlet extraction process for pre-separating the light rare earth ore disclosed by the invention is improved by 26%, the total volume of an extraction tank body is reduced by 25%, the storage amount of an extracting agent and rare earth metals in the extraction tank is reduced by 24%, the amount of acid-base chemical raw materials is also reduced by 19%, the production and operation cost is reduced, the wastewater discharge is reduced, and the environment friendliness is facilitated.
Example 2.
The light rare earth ore is prepared by dissolving, purifying, proportioning and chlorinatingThe rare earth concentration of the rare earth solution is 1.7 mol.L-1And the pH value is ﹦ 2-3, and the rare earth is distributed as follows:
Figure 350563DEST_PATH_IMAGE002
。
the organic phase consists of an extracting agent P507 (2-ethylhexyl phosphate mono-2-ethylhexyl ester) and a diluting agent kerosene, and the concentration of the P507 in the organic phase is 1.5 mol.L-1The saponification concentration of P507 was 0.54 mol. L-1. The loaded organic phase pre-separation five-outlet extraction process of the invention is adopted in the embodiment 2, the process flow schematic diagram of the process is shown in the attached figure 2, and the process is implemented according to the specific technical scheme steps of the embodiment 2.
Through the embodiment 2 of the five-outlet extraction process for pre-separating the loaded organic phase of the light rare earth ore, 99.5 percent of pure Sm product and four enrichments of La-Nd, SmEuGd, GdTbDy and Ho-LuY can be obtained after extraction and separation.
Through measurement and calculation, compared with the traditional extraction separation process, the extraction separation effect of the embodiment 2 of the loaded organic phase pre-separation five-outlet extraction process for pre-separating the light rare earth ore disclosed by the invention is improved by 25%, the total volume of an extraction tank body is reduced by 24%, the storage amount of an extracting agent and rare earth metals in the extraction tank is reduced by 24%, the amount of acid-base chemical raw materials is also reduced by 19%, the production and operation cost is reduced, the wastewater discharge is reduced, and the environment friendliness is facilitated.
Example 3.
The light rare earth ore is prepared from rare earth chloride solution of rare earth ore from Shandong Weishan mountain through dissolving, purifying and proportioning, and the rare earth concentration of the rare earth chloride solution is 1.5 mol.L-1And the pH value is ﹦ 2-3, and the rare earth is distributed as follows:
Figure 130300DEST_PATH_IMAGE003
。
the organic phase is extracted by an extractant P507(2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester) and a diluent kerosene, P in the organic phase507The concentration is 1.5 mol.L-1，P507The saponification concentration was 0.58 mol. L-1. The La-Nd light rare earth pre-separation three-outlet extraction separation process has the process flow schematic diagram shown in attached figure 1 and is implemented according to the specific implementation mode of the invention.
By the embodiment 3 of the loaded organic phase pre-separation five-outlet extraction process for pre-separating the light rare earth ore, 98 percent of pure Sm product and four enrichments of La-Nd, SmEuGd, GdTbDy and Ho-LuY can be obtained after extraction and separation.
Through measurement and calculation, compared with the traditional extraction separation process, the extraction separation effect of the embodiment 3 of the loaded organic phase pre-separation five-outlet extraction process for pre-separating the light rare earth ore disclosed by the invention is improved by 23%, the total volume of an extraction tank body is reduced by 23%, the storage amount of an extracting agent and rare earth metals in the extraction tank is reduced by 22%, the amount of acid-base chemical raw materials is also reduced by 19%, the production and operation cost is reduced, the wastewater discharge is reduced, and the environment friendliness is facilitated.

Claims (6)

1. A loaded organic phase pre-separation five-outlet extraction process for pre-separating light rare earth ore is characterized in that: an outlet organic phase loaded Sm-LuY of the light rare earth ore subjected to pre-separation countercurrent extraction and a small amount of La-Nd rare earth as organic materials enter a pre-separation washing process, an outlet water phase and an outlet organic phase after pre-separation washing enter a La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process, and the five-outlet process obtains a pure Sm product and four components of La-Nd, SmEuGd, GdTbDy and Ho-LuY; the specific technical scheme is as follows: the pre-dividing and washing process consists of a pre-dividing and washing front section and a pre-dividing and washing rear section, and is characterized in that part of an outlet organic phase of the pre-dividing and washing front section flows into the five-outlet process from a position between a SmEuGd outlet and a GdTbDy outlet of the five-outlet process; or the pre-dividing washing process consists of a pre-dividing washing front section and a pre-dividing washing rear section, and is characterized in that part of outlet organic phase of the pre-dividing washing front section flows into the five-outlet process from a pure Sm outlet and a SmEuGd outlet of the five-outlet process; or the outlet organic phase of the pre-separation washing section flows into the five-outlet process from the position between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process; these three embodiments are as follows:
scheme 1: the organic phase at the outlet of the pre-separation washing front section part flows into the space between SmEuGd and GdTbDy outlets of the five outlets
The pre-separation washing section of the embodiment 1 is a countercurrent washing process and comprises a pre-separation washing front section and a pre-separation washing rear section, and is characterized in that part of an outlet organic phase of the pre-separation washing front section flows into a five-outlet process from a position between a SmEuGd outlet and a GdTbDy outlet of the five-outlet process, and the technical scheme comprises the following steps: (1) after the light rare earth ore is subjected to pre-partition countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth are taken as organic materials to flow into the 1 st stage of the pre-partition washing front section and an outlet aqueous phase from the pre-partition washing rear section for countercurrent washing; (2) part of the organic phase at the outlet of the pre-separation washing front section flows into the pre-separation washing rear section and is subjected to countercurrent washing with washing acid flowing in from the last stage, namely the nth stage, of the pre-separation washing rear section, and the water phase at the outlet of the pre-separation washing rear section flows into the last stage of the pre-separation washing front section; (3) the water phase at the 1 st stage outlet of the pre-separating and washing front stage flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, the other part of the organic phase at the outlet of the pre-separating and washing front stage flows into the five-outlet process from the position between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process, and the organic phase at the n th stage outlet of the pre-separating and washing rear stage flows into the five-outlet process from the position between the organic phase at the last outlet of the five-; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99.5%, and SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet;
scheme 2: part of the outlet organic phase at the front stage of pre-separation washing flows into the part of the outlet of the pre-separation washing from the part between pure Sm and GdTbDy outlets of the five outlets
The pre-divided washing section of the embodiment 2 is a countercurrent washing process which comprises a pre-divided washing front section and a pre-divided washing rear section, and is characterized in that part of an outlet organic phase of the pre-divided washing front section flows into a five-outlet process from a pure Sm outlet and a SmEuGd outlet of the five-outlet process, and the technical scheme comprises the following steps: (1) after the light rare earth ore is subjected to pre-partition countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth are taken as organic materials to flow into the 1 st stage of the pre-partition washing front section and an outlet aqueous phase from the pre-partition washing rear section for countercurrent washing; (2) part of the organic phase at the outlet of the pre-separation washing front section flows into the pre-separation washing rear section and is subjected to countercurrent washing with washing acid flowing in from the last stage, namely the nth stage, of the pre-separation washing rear section, and the water phase at the outlet of the pre-separation washing rear section flows into the last stage of the pre-separation washing front section; (3) the water phase at the 1 st stage outlet of the pre-separation washing front stage flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, the other part of the organic phase at the outlet of the pre-separation washing front stage flows into the five-outlet process from the position between the pure Sm outlet and the SmEuGd outlet of the five-outlet process, and the organic phase at the n th stage outlet of the pre-separation washing rear stage flows into the five-outlet process from the position between the organic phase at the last outlet of the five-outlet process and the G; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99.5%, and SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet;
scheme 3: the outlet organic phase of the pre-separation washing section flows into the space between the outlets of the five-outlet process SmEuGd and GdTbDy
The pre-divided washing section of this embodiment 3 is a counter current washing process, the technical scheme of which comprises the steps of: (1) after the light rare earth ore is subjected to pre-separation countercurrent extraction, Sm-LuY loaded on an outlet organic phase and a small amount of La-Nd rare earth serving as organic materials flow into the washing acid entering the 1 st stage and the nth stage of the pre-separation washing section for countercurrent washing; (2) the water phase at the 1 st stage outlet of the pre-separation washing section flows into the five-outlet process from the position between the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process and the pure Sm outlet, and the organic phase at the outlet of the pre-separation washing section flows into the five-outlet process from the position between the SmEuGd outlet and the GdTbDy outlet of the five-outlet process; making the alkali saponification organic phase flow into a front rare earth soap section of a five-outlet process, and using part of outlet water phase La-Nd of the five-outlet process to perform rare earth soap, wherein the prepared La-Nd rare earth soap organic phase flows into the outlet water phase of the five-outlet process in a level manner; or the La-Nd rare earth soap organic phase prepared by other methods by using part of the outlet water phase La-Nd rare earth of the five-outlet process flows into the extraction organic phase of the five-outlet process from the outlet water phase level; the water phase at the outlet of the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process is La-Nd rare earth with Sm less than a control index, the organic phase at the outlet is Ho-LuY rare earth, Sm at the No. 3 outlet, namely a pure Sm outlet, is 97-99%, and SmEuGd and GdTbDy enrichments are respectively obtained at the No. 4 outlet and the No. 5 outlet.
2. The process of claim 1, wherein the light rare earth ore comprises: bastnaesite, monazite, cerium niobium perovskite, southern ion light rare earth ore, one of these ores, or a combination of these ores; the light rare earth ore is produced by Baotou, Sichuan crown Ning, Shandong Weishan and Guangdong Shanhai.
3. The process of claim 1, wherein the pre-split washing process and the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process are a hydrochloric acid system or a nitric acid system or a sulfuric acid system.
4. The process of claim 1, wherein Sm-LuY and a small amount of La-Nd rare earth are loaded on the outlet organic phase of the light rare earth ore subjected to pre-divided countercurrent extraction, and the content of La-Nd rare earth in the loaded rare earth is greatly reduced compared with that in the light rare earth ore.
5. The process of claim 1, wherein the organic phase at the outlet of the pre-dividing washing front section is divided into two parts, one part of the organic phase flows into the pre-dividing washing rear section, and the other part of the organic phase flows into the La-Nd/Sm/SmEuGd/GdTbDy/Ho-LuY five-outlet process; the two organic phases must be controlled in their flow rate, or at least in one of them.
6. The process of claim 1, wherein the organic phase is composed of an extractant and a diluent, the extractant is 2-ethylhexyl 2-phosphate mono (also known as HEH EHP, or P507) or di (2-ethylhexyl) phosphate (also known as HDEHP, or P204), and the concentration of the extractant in the organic phase is 0.8 to 1.6 mol-L "1; the diluent is kerosene or n-hexane organic solvent.
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