CN115679130A - A kind of grouping method of ionic rare earth ore erbium and thulium - Google Patents

Abstract

The invention relates to an ion type rare earth ore erbium thulium grouping method, and belongs to the technical field of rare earth extraction separation. The invention provides an erbium-thulium grouping method for ionic rare earth ore, which solves the problem of lutetium and other heavy rare earth loss in the existing ionic rare earth ore grouping process, and comprises the steps of carrying out erbium-thulium grouping by adopting a P507-isooctanol system in the first step, simulating fractional extraction by using a separating funnel method, wherein the total content of thulium, ytterbium and lutetium in outlet organic phase rare earth is more than 99%, the content of thulium, ytterbium and lutetium in outlet aqueous phase rare earth is less than 0.03%, and the high yield of lutetium and other heavy rare earth is ensured. Compared with the existing grouping process, the method has the advantages of short flow, high yield, low acid consumption, easy realization of industrialization and the like, and has practical application value.

Description

A kind of grouping method of ionic rare earth ore erbium and thulium

technical field

The invention belongs to the technical field of rare earth extraction and separation, and in particular relates to a grouping method of ion-type rare earth ore erbium and thulium.

Background technique

Ionic minerals have a complete distribution of rare earths, mainly medium and heavy rare earths, and are rich in medium and heavy rare earth elements such as europium, terbium, dysprosium, erbium, lutetium, and yttrium required for functional materials. They are unique strategic resources in my country. Ionic rare earth ores are mainly distributed in Jiangxi, Fujian, Guangdong, Hunan, Guangxi and other provinces in southern my country. According to the distribution characteristics of rare earth ores, they can be divided into light rare earth type, medium yttrium rich europium type and high yttrium type, thulium oxide, The total amount of ytterbium oxide and lutetium oxide is about 0.9%, 1.6%, and 4.4% in the three types of ion-type minerals, respectively. At present, the main process of rare earth separation of ion-type ore adopts P507 (2-ethylhexylphosphonic acid mono-2-ethylhexyl ester) and naphthenic acid system, and ion-type rare earth ore can only be obtained from thulium, ytterbium and lutetium concentrates after many times of grouping (Sep. Purif. Technol., 2017, 184, 280-287.). For example, high-yttrium-rich ion ores first use naphthenic acid to separate yttrium oxide, and then group erbium and thulium through the P507 system to obtain thulium, ytterbium and lutetium concentrates; medium-yttrium-europium-rich ion ores first pass the P507 system dysprosium and holmium grouping to obtain holmium-lutetium Concentrates (Ho, Er, Tm, Yb, Lu, Y), and then separate yttrium oxide through naphthenic acid system, and finally use P507 to group holmium-lutetium enrichment erbium and thulium to obtain thulium, ytterbium and lutetium enrichment; The light rare earth ion ore uses the P507 system to group neodymium, samarium and dysprosium and holmium in sequence, and naphthenic acid to separate yttrium oxide, and finally uses the P507 system to group erbium and thulium to obtain thulium, ytterbium and lutetium concentrates. There are some problems in the existing grouping of ionic rare earth ores. For example, the process of obtaining thulium, ytterbium and lutetium concentrates is relatively long, and the P507 system is incomplete for the back extraction of heavy rare earths such as thulium, ytterbium and lutetium. The yield of thulium, ytterbium and lutetium in the grouping process is about 95%. , It is easy to cause problems such as the loss of valuable heavy rare earth resources such as lutetium.

Contents of the invention

The present invention aims to solve the technical problems in the prior art, and provides a method for grouping erbium and thulium of ion-type rare earth ore, adopting the P507-isooctanol system to carry out grouping of erbium and thulium, and simulating fractionation extraction through a separating funnel method, so that the grouping of erbium and thulium can be exported The total content of thulium, ytterbium and lutetium in the rare earth organic phase is greater than 99%, and the content of thulium, ytterbium and lutetium in the outlet water phase is less than 0.03%, which ensures a high yield of heavy rare earths such as lutetium, and the organic phase containing thulium, ytterbium and lutetium concentrates can be Lutetium oxide, thulium oxide and ytterbium oxide are directly separated by the organic phase feeding method.

In order to solve the problems of the technologies described above, the technical solution of the present invention is specifically as follows:

The invention provides a method for grouping ionic rare earth ore erbium and thulium, comprising the following steps:

According to the distribution characteristics of different types of ionic rare earth ores, the cascade extraction theory is used to determine the number of stages and the flow ratio; the separating funnel method is used to simulate fractional distillation extraction, and the erbium and thulium grouping process consists of n-stage extraction and m-stage washing; The organic phase, the feed liquid of the nth stage, and the washing acid of the n+mth stage, after shaking, stand still for phase separation and fractional distillation; n and m are positive integers.

In the above technical solution, the organic phase has a concentration of 1.2-1.5 mol/LP507, 10-30% iso-octanol, and a saponification rate of 36%.

In the above technical solution, n is 13-14, and m is 8-11.

In the above technical solution, the acidity pH of the water phase in the further grouping method is 0.60-1.50.

In the above technical solution, the grouping method of the present invention is actually applied in the industrial production process. Due to the influence of factors such as extraction tank level efficiency, the actual number of extraction stages n and the number of washing stages m are 1.5 to 3 times of theoretical calculations.

In the above technical solution, the different types of ionic rare earth minerals are light rare earth type, medium yttrium rich in europium type or high yttrium type.

The beneficial effects of the present invention are:

(1) The present invention provides a method for grouping erbium and thulium of ionic rare earth ore. In the first step, the P507-isooctanol system is used to group erbium and thulium to obtain precious thulium, ytterbium and lutetium, and the yield of thulium, ytterbium and lutetium is greater than 99%. Compared with the yield of about 95% of thulium, ytterbium and lutetium in the P507 system after more than two steps of grouping, the present invention can obtain thulium, ytterbium and lutetium concentrates in one step, and has the advantages of short process and high yield.

(2) Compared with the hydrochloric acid concentration of the existing P507 system erbium-thulium grouping water phase of 0.40～1.10mol/L, the acidity range of the P507-isooctanol system erbium-thulium grouping water phase of the present invention is pH 0.60～1.50, which greatly reduces the concentration of the water phase Acidity, reduces acid consumption.

(3) P507-isooctanol system separation of lutetium oxide has been industrialized production, ionic rare earth ore using P507-isooctanol system erbium thulium grouping, the organic phase containing thulium ytterbium lutetium can be directly fed, and can be combined with existing lutetium oxide Equal-heavy rare earth separation process is connected, easy to realize industrialization, and has practical application value.

Description of drawings

The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.

Figure 1 shows the results of cascade simulation experiments for the concentration of rare earths in the aqueous and organic phases and the acidity of the aqueous phase.

Detailed ways

The inventive idea of the present invention is: the ionic rare earth ore adopts the rare earth separation process with ammoniated P507 and naphthenic acid as the main technology, which has been widely used in the rare earth hydrometallurgy industry in my country, and has achieved good economic and social benefits . In recent years, in view of the key technical problems of the P507 system in the separation process of thulium, ytterbium and lutetium heavy rare earths, such as low separation efficiency of thulium, ytterbium and lutetium heavy rare earths, incomplete stripping, and difficulty in preparing high-purity products, the research group invented "an additive improved "Separation of Heavy Rare Earths by Extraction System of Reagents" (ZL200510016682.6), developed a new extraction system superior to P507 for separation of heavy rare earths, the separation selectivity of the new system in terms of Tm, Yb, Lu, stripping acidity, especially easy stripping Complete and other aspects are superior to the P507 system, which has laid a foundation for the application of high-purity lutetium high-efficiency separation technology. Using this patented technology, a number of leading enterprises in the separation of heavy rare earths have built a production line for the separation of heavy rare earths in southern ionic ore, and realized the industrial production of lutetium oxide for crystals. Thulium, ytterbium and lutetium concentrates can only be obtained after multiple groupings of ionic rare earth ores by systems such as P507. Due to the incomplete stripping of heavy rare earths such as thulium, ytterbium and lutetium by the P507 system, heavy rare earth resources such as lutetium are lost in the grouping process. In order to solve the problem of loss of heavy rare earths such as lutetium in the existing ionic rare earth ore grouping process, the present invention proposes a method for grouping erbium and thulium in the ion type rare earth ore. The liquid funnel method simulates fractional distillation extraction, so that the total content of thulium, ytterbium and lutetium in the rare earths in the organic phase of erbium and thulium grouping is greater than 99%, and the content of thulium, ytterbium and lutetium in the exporting water phase rare earths is less than 0.03%, which ensures a higher recovery of heavy rare earths such as lutetium. rate, the organic phase containing thulium, ytterbium and lutetium concentrates can be directly separated from lutetium oxide, thulium oxide and ytterbium oxide by using the organic phase feeding method.

The present invention proposes a method for grouping ionic rare earth ore erbium and thulium, which specifically includes:

According to the distribution characteristics of different types of ionic rare earth ores, the cascade extraction theory is used to determine the number of stages and flow ratio. The "separating funnel method" is used to simulate fractional distillation extraction, and the erbium and thulium grouping process consists of n-stage extraction and m-stage washing. The first stage enters the organic phase, the nth stage feeds the liquid, and the n+m stage enters the washing acid. After shaking for 30 minutes, stand still for phase separation and fractional distillation.

In the present invention: different types of ionic minerals mainly include light rare earth type, medium yttrium rich europium type and high yttrium type; organic phase is: 1.2～1.5mol/LP507 concentration, 10～30% isooctyl alcohol, saponification rate is 36 %; n is 13-14, and m is 8-11; further, the acidity pH of the water phase in the grouping method is 0.60-1.50.

When the grouping method of the present invention is actually applied in the industrial production process, the actual number of extraction stages n and the number of washing stages m should be 1.5 to 3 times of theoretical calculations. The different types of ionic rare earth minerals are light rare earth type, medium yttrium rich europium type or high yttrium type.

Example 1

Taking the erbium-thulium grouping of a high-yttrium-type ion ore as an example, the composition of the feed solution is shown in Table 1. The molar fraction of the thulium group is 3.81%, and the molar fraction of the erbium group is 96.19%. The number of stages and the flow ratio are determined by cascade extraction theory. The "separating funnel method" is used to simulate fractional distillation extraction, and the erbium-thulium grouping process consists of 14 stages of extraction and 8 stages of washing. The first stage enters the organic phase, the 14th stage feeds liquid, and the 22nd stage enters the washing acid. After shaking for 30 minutes, stand still for phase separation and fractional distillation. Organic phase: 1.2mol/L P507+15% isooctyl alcohol, saponification rate 36%; aqueous phase: [RE ³⁺ ]=1.2mol/L, pH=0.52; washing acid: 4.5mol/L HCl. The flow ratio is organic phase: feed liquid: washing acid = 6.67:1:0.55. The results of the cascade simulation experiment show that the total content of thulium, ytterbium and lutetium in the export organic phase rare earth is increased to 99.21%, the yttrium oxide in the export organic phase rare earth is 0.79%, and the thulium, ytterbium and lutetium in the export water phase rare earth is less than 0.03%. The results of the concentration of rare earths in the organic phase and water phase and the acidity of the water phase are shown in Figure 1. The optimum acidity of the water phase in the cascade simulation experiment is pH 0.90-1.45.

Table 1 Distribution of rare earth elements in high-yttrium ion ores (%)

Example 2

Taking the erbium-thulium grouping of a light rare earth ion ore as an example, the composition of the feed solution is shown in Table 2, in which the molar fraction of the thulium group is 0.88%, and the molar fraction of the erbium group is 99.12%. The series number and flow ratio are determined by cascade extraction theory. The "separating funnel method" is used to simulate fractional distillation extraction, and the erbium and thulium grouping process consists of 14 stages of extraction and 11 stages of washing. The first stage enters the organic phase, the 14th stage feeds the liquid, and the 25th stage enters the washing acid. After shaking for 30 minutes, stand still for phase separation and fractional distillation. Organic phase: 1.2 mol/L P507+10% isooctyl alcohol, saponification rate 36%; aqueous phase: [RE ³⁺ ]=1.0 mol/L, pH=0.40; washing acid: 4.5 mol/L HCl. The flow ratio is organic phase: feed liquid: washing acid = 5.37:1:0.46. The results of cascade simulation experiments show that the total content of thulium, ytterbium and lutetium in the export organic phase rare earth is greater than 99.60%, the content of erbium group in the export organic phase rare earth is less than 0.4%, and the thulium, ytterbium and lutetium in the export water phase rare earth is less than 0.03%. The optimal acidity of water phase in cascade simulation experiment is pH 0.80-1.50.

Table 2 Distribution of rare earth elements in light rare earth ion ores (%)

Example 3

Taking the erbium-thulium grouping of a medium-yttrium-europium-rich ion ore as an example, the composition of the feed solution is shown in Table 3, wherein the molar fraction of the thulium group is 2.52%, and the molar fraction of the erbium group is 97.48%. Compare. The "separating funnel method" is used to simulate fractional distillation extraction, and the erbium and thulium grouping process consists of 13 stages of extraction and 9 stages of washing. The first stage enters the organic phase, the 13th stage feeds the liquid, and the 22nd stage enters the washing acid. After shaking for 30 minutes, stand still for phase separation and fractional distillation. Organic phase: 1.5mol/L P507+20% isooctyl alcohol, saponification rate 36%; aqueous phase: [RE ³⁺ ]=1.0mol/L, pH=0.60; washing acid: 4.5mol/L HCl. The flow ratio is organic phase: feed liquid: washing acid = 5.10:1:0.46. The results of cascade simulation experiments show that the total content of thulium, ytterbium and lutetium in the export organic phase rare earth is more than 99.50%, the content of erbium group in the export organic phase rare earth is less than 0.5%, and the thulium, ytterbium and lutetium in the export water phase rare earth is less than 0.03%. The optimal acidity of water phase in cascade simulation experiment is pH 0.60-1.40.

Distribution of rare earth elements in yttrium and europium-rich ion ores in Table 3 (%)

Example 4

Taking the erbium-thulium grouping of a light rare earth ion ore as an example, the molar distribution of the thulium group is 0.88%, and the molar distribution of the erbium group is 99.12%. The series number and flow ratio are determined by cascade extraction theory. The "separating funnel method" is used to simulate fractional distillation extraction, and the erbium and thulium grouping process consists of 14 stages of extraction and 11 stages of washing. The first stage enters the organic phase, the 14th stage feeds the liquid, and the 25th stage enters the washing acid. After shaking for 30 minutes, stand still for phase separation and fractional distillation. Organic phase: 1.5 mol/L P507, saponification rate 36%; aqueous phase: [RE ³⁺ ]=1.0 mol/L, pH=1.0; washing acid: 4.5 mol/L HCl. The flow ratio is organic phase: feed liquid: washing acid = 3.88:1:0.46. The results of cascade simulation experiments show that the total content of thulium, ytterbium and lutetium in the export organic phase rare earth is more than 99%, the content of erbium group in the export organic phase rare earth is less than 1%, and the thulium, ytterbium and lutetium in the export water phase rare earth is less than 0.05%. The optimal acidity of water phase in cascade simulation experiment is 0.40～1.10mol/L.

Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. And the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.

Claims (6)

1. an ion type rare earth ore erbium thulium grouping method is characterized in that, comprises the following steps: According to the distribution characteristics of different types of ionic rare earth ores, the cascade extraction theory is used to determine the number of stages and the flow ratio; the separating funnel method is used to simulate fractional distillation extraction, and the erbium and thulium grouping process consists of n-stage extraction and m-stage washing; The organic phase, the feed liquid of the nth stage, and the washing acid of the n+mth stage, after shaking, stand still for phase separation and fractional distillation; n and m are positive integers. 2. The grouping method of ionic rare earth ore erbium and thulium according to claim 1, wherein the organic phase is: 1.2 to 1.5 mol/LP507 concentration, 10 to 30% isooctyl alcohol, and a saponification rate of 36%. 3. the ionic rare earth ore erbium-thulium grouping method according to claim 1, is characterized in that, n is 13-14, and m is 8-11. 4. The grouping method of ionic rare earth ore erbium and thulium according to claim 1, characterized in that, the aqueous phase acidity pH of the grouping method is 0.60-1.50. 5. ionic rare earth ore erbium-thulium grouping method according to claim 1, is characterized in that, described grouping method is actually applied in industrial production process, and actual extraction stage number n and washing stage number m should be 1.5 of theoretical calculation. ~3 times. 6. The method for grouping erbium-thulium ionic rare earth ores according to claim 1, wherein the different types of ionic rare earth ores are light rare earth type, medium yttrium rich in europium type or high yttrium type.

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