A cerium soap organic phase and its preparation method and application

Abstract

The present invention provides a cerium soap organic phase and its preparation method and application, the preparation method comprises: (1) extracting an organic phase containing Ce with an extractant; 4+ The aqueous solution was extracted to obtain Ce 4+ (2) Ce-containing organic phase 4+ Ce in the organic phase 4+ Reduction was performed to obtain Ce 3+ The organic phase of cerium soap. 4+ The coordination effect with the extractant is very strong. The present invention makes full use of Ce 4+ Easy to extract, Ce can be achieved without saponification 4+ Extraction; containing Ce 4+ The organic phase containing Ce can be prepared by reduction 3+ The cerium soap organic phase avoids the consumption of alkaline substances and the generation of saline wastewater from the source.

Description

Technical Field

[0001] The invention belongs to the field of rare earth separation and relates to a cerium soap organic phase, in particular to a cerium soap organic phase and a preparation method and application thereof. Background Art

[0002] In the process of extraction and separation using acidic extractants, the organic phase needs to be saponified in order to enhance the extraction capacity. There are many types of saponifiers used in the extraction and saponification process, including sodium hydroxide, ammonia water, calcium oxide, magnesium bicarbonate, and lanthanum carbonate. The saponification process not only consumes a large amount of alkali, but also produces a large amount of salt-containing wastewater, increasing the cost of reagent consumption and environmental treatment. Therefore, the recycling of saponifiers has great economic value. When ammonia water is used as a saponifier, the ammonium chloride solution produced is generally reused by adding calcium oxide to volatilize the ammonia. Although this method achieves the regeneration of the saponifier, it still produces wastewater containing calcium chloride.

[0003] Patent CN1249259C discloses a method for extracting and separating rare earth carbonate and rare earth oxide using an acidic extractant. This method utilizes the hydrogen ions in P507 to dissolve the rare earth carbonate or rare earth oxide concentrate. This process eliminates the need for hydrochloric acid to dissolve the material and the need for alkaline solution to saponify the organic phase, saving both acid and alkali. However, due to the low acidity of P507, insufficient dissolution of the rare earth concentrate can result in the introduction of small particles into the extraction tank, leading to the formation of a third phase and compromising the separation effect.

[0004] CN100486666 discloses a method for preparing an ammonia-calcium composite saponifier and conducting continuous saponification extraction. This method involves mixing an ammonium salt solution with lime to prepare an ammonia-calcium composite solution. After filtration or clarification, the ammonia-calcium composite clear solution is obtained. The clear solution and an organic phase are then continuously saponified. The loaded organic phase is then countercurrently washed with a calcium salt solution in 1-10 extraction tanks for deammoniation. The saponified organic phase is then mixed with the solution to be extracted for extraction, separation, and back extraction. However, this method produces wastewater with a high salinity, which is detrimental to environmental protection. Furthermore, the extraction process produces ammonia nitrogen wastewater, which is expensive to treat.

[0005] The traditional extractive saponification process utilizes the acidity of the extractant to form a salt by adding an alkaline substance, allowing for a more thorough extraction process. However, this process inevitably consumes a large amount of alkali and produces saline wastewater. To achieve a clean and efficient saponification process, the development of a novel method for preparing the organic phase of cerium soap is crucial. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the present invention aims to provide a cerium soap organic phase and its preparation method and application. 4+The coordination effect with the extractant is very strong, and Ce can be achieved without saponification. 4+ Extraction; containing Ce 4+ The organic phase containing Ce can be prepared by reduction 3+ The organic phase of cerium soap can avoid the consumption of alkaline substances and the generation of salt-containing wastewater from the source.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing a cerium soap organic phase, the preparation method comprising the following steps:

[0009] (1) Using an organic phase containing an extractant to react with Ce 4+ The aqueous solution was extracted to obtain Ce 4+ of the organic phase;

[0010] (2) For Ce-containing 4+ Ce in the organic phase 4+ Reduction was performed to obtain Ce 3+ of cerium soap organic phase.

[0011] Because Ce 4+ The coordination effect with the extractant is very strong. The present invention makes full use of Ce 4+ Easy to extract, Ce can be achieved without saponification 4+ Extraction. Contains Ce 4+ The organic phase containing Ce can be prepared by reduction 3+ The cerium soap organic phase avoids the consumption of alkaline substances and the generation of saline wastewater from the source.

[0012] The cerium of the present invention has a variable valence property and contains Ce 3+ After the extraction operation, the organic phase of cerium soap containing Ce is obtained. 3+ The aqueous solution containing Ce can be obtained after oxidation 4+ The aqueous solution containing Ce 4+ The aqueous solution was extracted to obtain Ce 4+ The organic phase containing Ce 4+ The organic phase was reduced to obtain Ce 3+ The cerium soap organic phase is obtained, thereby realizing the recycling of the cerium soap organic phase.

[0013] The extractant in the organic phase containing the extractant includes a phosphorus-containing extractant or a carboxylic acid extractant.

[0014] Preferably, the phosphorus-containing extractant includes any one of P204, P507 or Cyanex272, or a combination of at least two thereof, for example, a combination of P204 and P507, a combination of P507 and Cyanex272, a combination of Cyanex272 and P204, or a combination of P204, P507 and Cyanex272.

[0015] Preferably, the carboxylic acid extractant includes any one of Versatic 10, CA-12 or cyclopentane acid, or a combination of at least two thereof, for example, a combination of Versatic 10 and CA-12, a combination of CA-12 and cyclopentane acid, a combination of cyclopentane acid and Versatic 10, or a combination of Versatic 10, CA-12 and cyclopentane acid.

[0016] Preferably, the volume fraction of the extractant in the organic phase containing the extractant in step (1) is not higher than 50%, for example, it can be 5%, 10%, 15%, 20%, 25%, 30%, 40% or 50%, but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0017] Preferably, the reduction in step (2) comprises chemical reduction.

[0018] Preferably, the reducing agent used in the chemical reduction includes any one of thiourea, hydrogen peroxide, sodium sulfite, sulfur dioxide, zinc powder, aldehyde or alcohol, or a combination of at least two thereof, for example, a combination of zinc powder and alcohol, a combination of zinc powder and aldehyde, a combination of sulfur dioxide and zinc powder, a combination of aldehyde and alcohol, a combination of sodium sulfite and glucose, a combination of glucose, fructose and thiourea, or a combination of sodium sulfite, zinc powder, aldehyde and alcohol.

[0019] Preferably, the Ce in the cerium soap organic phase in step (2) 3+ The concentration is not less than 0.05 mol / L, for example, it can be 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.18 mol / L, 0.2 mol / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] Preferably, as a preferred technical solution of the preparation method described in the first aspect, the preparation method comprises the following steps:

[0021] (1) The organic phase containing Ce is not higher than 50% by volume of the extractant. 4+ The aqueous solution was extracted to obtain Ce 4+ an organic phase, wherein the extractant is P204, P507, Cyanex 272, Versatic 10, cyclohexane acid or CA-12;

[0022] (2) For Ce-containing 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of the cerium soap organic phase is not less than 0.05 mol / L.

[0023] In a second aspect, the present invention provides a cerium soap organic phase, which is obtained by the preparation method described in the first aspect.

[0024] In a third aspect, the present invention provides a use of the cerium soap organic phase described in the second aspect, wherein the cerium soap organic phase is used for extraction.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] Because Ce 4+ The coordination effect with the extractant is very strong. The present invention makes full use of Ce 4+ Easy to extract, Ce can be achieved without saponification 4+ Extraction. Contains Ce 4+ The organic phase containing Ce can be prepared by reduction 3+ The organic phase of cerium soap avoids the consumption of alkaline substances and the generation of saline wastewater from the source;

[0027] The cerium of the present invention has a variable valence property and contains Ce 3+ After the extraction operation, the organic phase of cerium soap containing Ce is obtained. 3+ The aqueous solution containing Ce can be obtained after oxidation 4+ The aqueous solution containing Ce 4+ The aqueous solution was extracted to obtain Ce 4+ The organic phase containing Ce 4+ The organic phase was reduced to obtain Ce 3+ The cerium soap organic phase is obtained, thereby realizing the recycling of the cerium soap organic phase. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0029] Example 1

[0030] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0031] (1) With an organic phase containing 20% ​​(V / V) P2O4 and Ce 4+ The Ce-containing4+ of the organic phase;

[0032] (2) Using glucose as a reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of cerium soap organic phase is 0.16 mol / L.

[0033] Example 2

[0034] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0035] (1) With an organic phase containing 5% (V / V) P507 and Ce 4+ The Ce-containing 4+ of the organic phase;

[0036] (2) Using zinc powder as a reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of cerium soap organic phase is 0.05mol / L.

[0037] Example 3

[0038] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0039] (1) Using an organic phase containing 15% (V / V) Cyanex272 and Ce 4+ The Ce-containing 4+ of the organic phase;

[0040] (2) Using hydrogen peroxide as a reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of cerium soap organic phase is 0.12mol / L.

[0041] Example 4

[0042] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0043] (1) An organic phase containing 50% (V / V) Versatic 10 and Ce 4+ The aqueous solution with a concentration of 0.5 mol / L was used for extraction, and the diluent in the organic phase was n-heptane to obtain Ce 4+ of the organic phase;

[0044] (2) Using sodium sulfite solution as a reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of cerium soap organic phase is 0.14mol / L.

[0045] Example 5

[0046] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0047] (1) Ce was present in an organic phase containing 15% (V / V) P507 and 20% (V / V) P204. 4+ The concentration of 1.5 mol / L aqueous solution was extracted to obtain Ce 4+ of the organic phase;

[0048] (2) Using formaldehyde as a reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of cerium soap organic phase is 0.2 mol / L.

[0049] Example 6

[0050] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0051] (1) Ce was present in an organic phase containing 25% (V / V) CA-12. 4+ The organic phase was extracted with a 0.9 mol / L aqueous solution, the volume ratio of the organic phase to the aqueous solution was 2:1, and Ce was obtained. 4+ of the organic phase;

[0052] (2) Using thiourea as a reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of cerium soap organic phase is 0.13 mol / L.

[0053] Example 7

[0054] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0055] (1) With an organic phase containing 15% (V / V) cyclohexane acid and Ce 4+ The organic phase was extracted with a 0.2 mol / L aqueous solution, the volume ratio of the organic phase to the aqueous solution was 1:1, and Ce was obtained. 4+ of the organic phase;

[0056] (2) Using formaldehyde and glucose mixed reagent as reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of cerium soap organic phase is 0.09 mol / L.

[0057] Example 8

[0058] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0059] (1) An organic phase containing 15% (V / V) cyclohexane acid and 10% (V / V) Versatic 10 was used to prepare a Ce-containing 4+ The Ce-containing 4+ of the organic phase;

[0060] (2) Using sulfur dioxide as a reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3 + The concentration of cerium soap organic phase is 0.12mol / L.

[0061] Example 9

[0062] This embodiment provides a method for preparing a cerium soap organic phase, the preparation method comprising:

[0063] (1) An organic phase containing 16% (V / V) P507 and 15% (V / V) cyclohexane acid was used to react with Ce. 4+ The Ce-containing 4+ of the organic phase;

[0064] (2) Using hydrogen peroxide as a reducing agent to reduce Ce 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of cerium soap organic phase is 0.08 mol / L.

[0065] The cerium soap organic phase obtained in Example 1-9 is Lu 3+ The concentration of 1 mol / L aqueous solution was used for extraction, and the volume ratio of the cerium soap organic phase to the aqueous solution was 6:1 to obtain Lu 3+ The extraction rates are shown in Table 1;

[0066] The cerium soap organic phase obtained in Example 1-9 was 3+The Sc was extracted with a 0.8 mol / L aqueous solution, and the volume ratio of the cerium soap organic phase to the aqueous solution was 5:1. 3+ The extraction rates are shown in Table 1.

[0067] Table 1

[0068] <![CDATA[Lu 3+ Extraction rate (%)]]> <![CDATA[Sc 3+ Extraction rate (%)]]> Example 1 94 98 Example 2 28 29 Example 3 80 82 Example 4 88 92 Example 5 99 99 Example 6 84 87 Example 7 75 78 Example 8 76 77 Example 9 84 85

[0069] From Table 1, we can get:

[0070] The cerium soap organic phase prepared by the preparation method of the cerium soap organic phase in Example 1-9 can be used for Lu 3+ Sc 3+ Plasma extraction.

[0071] In summary, due to Ce 4+ The coordination effect with the extractant is very strong. The present invention makes full use of Ce 4+ Easy to extract, Ce can be achieved without saponification 4+ Extraction. Contains Ce 4+ The organic phase containing Ce can be prepared by reduction 3+ The cerium soap organic phase avoids the consumption of alkaline substances and the generation of saline wastewater from the source; the cerium of the present invention has a variable valence characteristic, containing Ce 3+ After the extraction operation, the organic phase of cerium soap containing Ce is obtained. 3+ The aqueous solution containing Ce can be obtained after oxidation 4+ The aqueous solution containing Ce 4+ The aqueous solution was extracted to obtain Ce 4+ The organic phase containing Ce 4+ The organic phase was reduced to obtain Ce 3+ The cerium soap organic phase is obtained, thereby realizing the recycling of the cerium soap organic phase.

[0072] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An application of a cerium soap organic phase, characterized in that, The preparation method of the cerium soap organic phase comprises the following steps: (1) The organic phase containing Ce is reacted with the extractant having a volume fraction of 15% to 50%. 4+ The aqueous solution was extracted to obtain Ce 4+ an organic phase, wherein the extractant is P204, P507, Cyanex 272, Versatic 10, cyclohexane acid or CA-12; (2) For Ce-containing 4+ Ce in the organic phase 4+ Chemical reduction is performed to obtain Ce 3+ The concentration of the cerium soap organic phase is not less than 0.12 mol / L; the reducing agent used in the chemical reduction includes any one of thiourea, hydrogen peroxide, sodium sulfite, sulfur dioxide, zinc powder, aldehyde or alcohol, or a combination of at least two thereof; The cerium soap organic phase is used for extraction, and after the extraction operation is completed, Ce-containing 3+ The aqueous solution containing Ce can be obtained after oxidation 4+ The aqueous solution is returned to step (1) for use.