Preparation method of solid extraction resin

Abstract

The invention discloses a preparation method of solid extraction resin, which comprises the following steps: preparing resin, and preparing 4M hydrochloric acid and 12M methanol as cleaning agents for cleaning the resin; adding resin and the cleaning agent according to a ratio of 1: 3 (g: ml); continuously contacting the resin with a cleaning agent to obtain cleaned resin; washing with hot water for several times, and washing hydrochloric acid and alcohol; drying at a high temperature to obtain a dried resin; stirring the dry resin and 30-80 vol% of an organic alcohol aqueous solution according to a ratio of 1: 50 (g: ml) so as to swell the dry resin into swollen resin; adding a metal extraction agent, and enabling the metal extraction agent to be in full contact with the swelling resin in a homogeneous phase; taking deionized water as a non-solvent, and adding the deionized water until the aqueous solution is turbid to generate phase separation; the organic alcohol and the metal extraction agent are subjected to rapid phase separation, so that the metal extraction agent is fixed in the resin, and then solid extraction resin is generated.

Description

Technical Field

[0001] The present invention relates to an extraction resin method, and more particularly to a method for preparing a solid-state extraction resin. The present invention also relates to a method for preparing a solid-state extraction resin by efficiently fixing a liquid extractant on a resin using a phase separation technique. Background Art

[0002] At present, Chinese patent CN1331607C discloses a method for preparing a strong acid anion exchange resin, and invents a method for preparing a sulfonated cross-linked poly(vinyl aromatic) copolymer, comprising (1) dehydrating a cross-linked poly(vinyl aromatic) copolymer prepared by water suspension polymerization to provide a dehydrated copolymer having a residual moisture content of 3-35%, based on the weight of the dehydrated copolymer; and (2) sulfonating the dehydrated copolymer at a temperature of 105°C-140°C for 20 minutes-20 hours in the presence of 95-105% sulfuric acid and in the absence of an organic swelling agent. The exchange resin can successfully manufacture a resin with specific adsorption properties and can adsorb specific extracts. However, since the preparation process of polymers with specific functional groups is complicated and the cost is relatively high, although the resin has specific adsorption functional groups, the application feasibility is limited.

[0003] In addition, Chinese patent CN103691146A discloses an impregnated resin extractant and a preparation method, which uses a polymer macroporous resin as a carrier to load a liquid extractant inside the macroporous resin, thereby changing the liquid / liquid extraction of rare metals or precious metals by the liquid extractant to liquid / solid extraction. The main manufacturing method comprises: (1) putting polyvinyl alcohol, sodium chloride and deionized water into a reaction container, starting to stir and completely dissolving all the raw materials; (2) after dissolution, heating the reaction system to 65-70°C; (3) mixing divinylbenzene, dibenzoyl peroxide, styrene and an extractant, and putting them into a reaction container, heating to 72-75°C; (4) keeping the reactor stirring, dispersing the oil phase into uniform beads; (5) after the dispersed beads are fixed, raising the temperature to 80°C and maintaining the temperature for 1 hour; (6) raising the temperature of the reaction system to 80°C and maintaining the temperature for 2-3 hours; (7) raising the temperature of the reaction system to 85°C and maintaining the temperature for 2-3 hours; (8) raising the temperature of the reaction system to 90°C and maintaining the temperature for 2-3 hours; (9) cooling the reaction system to below 50°C, filtering out the resin; (10) washing the resin with tap water, and obtaining the finished product of the impregnated resin extractant of the present invention.

[0004] Although the impregnation resin synthesis method can also fix the extractant in the resin, the operation steps are complicated and require multiple stages of heating and temperature holding to maintain the stability of the beads, which will increase the difficulty of process design for industry personnel.

[0005] Therefore, how to solve the above problems and defects of the prior art has become a research and development topic that relevant industry personnel are eager to research and develop. Summary of the invention

[0006] The object of the present invention is to provide a method for preparing a solid-state extraction resin, and to prepare the solid-state extraction resin in a simpler preparation manner.

[0007] The present invention provides a method for preparing a solid-state extraction resin, which comprises the following steps: S11: preparing a resin, and preparing 4M hydrochloric acid and 12M methanol as a cleaning agent for cleaning the resin; S12: adding the resin and the cleaning agent at a ratio of 1:3 (g:ml); S13: making the resin and the cleaning agent contact continuously to obtain a cleaned resin; S14: washing with hot water for several times to clean the hydrochloric acid and methanol; S15: drying at high temperature to obtain a dried resin; S21: The dry resin is stirred with 30-80 vol% of an organic alcohol at a ratio of 1:50 (g:ml), thereby swelling the dry resin into a swollen resin; S22: adding a metal extractant, and making the metal extractant fully contact with the swollen resin in a homogeneous phase; S31: using a deionized water as a non-solvent, adding pure water after step S22 until the aqueous solution is turbid to produce phase separation; and S32: allowing the organic alcohol and the metal extractant to undergo rapid phase separation, so that the metal extractant is fixed in the resin, thereby producing a solid extraction resin. Steps S11, S12, S13, S14 and S15 are cleaning stages, steps S21 and S22 are solvent treatment stages, and steps S31 and S32 are non-solvent treatment stages. In step S22, the solution composition range at this time is in a "homogeneous phase (clear)" area. In step S32, the solution composition range at this time is in a "phase separation (separation)" area.

[0008] In one embodiment of the present invention, the resin in step S11 is a porous resin.

[0009] In one embodiment of the present invention, the resin in step S11 is characterized by a polymer adsorbent that uses styrene as a monomer and is polymerized with other cross-linking agents.

[0010] In one embodiment of the present invention, the organic alcohol is used as a swelling agent.

[0011] In one embodiment of the present invention, the metal extractant is an acid extractant, an acid chelating extractant, an anionic extractant or a solvent extractant.

[0012] In one embodiment of the present invention, the metal extractant is one of di(2-ethylhexyl)phosphoric acid (D2EHPA), mono-2-ethylhexyl(2-ethylhexyl)phosphonate (PC88A), and trioctyl methyl ammonium chloride (Aliquat 336).

[0013] In one embodiment of the present invention, the immobilized content of the metal extractant is 0.5-3 mmol / g.

[0014] In the present invention, "vol%" means "volume%".

[0015] In summary, the preparation method of the solid-state extraction resin disclosed in the present invention can achieve the following effects:

[0016] 1. The extraction effect can be improved by selecting different extractants according to different targets;

[0017] 2. It is fixed in the pores of the carrier, and the immobilized extractant has good stability in the carrier; and

[0018] 3. The solid-state extraction resin can still maintain its extraction effect after multiple extraction / regeneration cycles.

[0019] The following detailed description is based on specific embodiments, so that the purpose, technical content, characteristics and effects of the present invention can be more easily understood. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The present invention is a flow chart of the method for preparing the solid-state extraction resin.

[0021] Figure 2 The figure is a detailed process flow chart of the preparation method of the solid extraction resin of the present invention.

[0022] Figure 3 It is a phase diagram of the preparation method of the solid extraction resin of the present invention.

[0023] 100: Preparation method of solid extraction resin; S110: Resin cleaning stage; S120: Solvent treatment stage; S130: Non-solvent treatment stage; S11, S12, S13, S14, S15, S21, S22, S31, S32: Steps. DETAILED DESCRIPTION

[0024] In order to solve the difficulty of process design of the existing impregnation resin synthesis method, the inventor has conducted many years of research and development to improve the shortcomings of existing products. The following will introduce in detail how the present invention uses a solid-state extraction resin preparation method to achieve the most efficient functional requirements.

[0025] The purpose of the present invention is to provide a method for preparing a solid-state extraction resin, which is prepared in a relatively simple preparation method. The extraction effect can be improved by selecting different extractants according to different targets, and then fixing them in the pores of a carrier. The immobilized extractant has good stability in the carrier, and the solid-state extraction resin can still maintain its extraction effect after multiple extraction / regeneration cycles. Since the present technology can select different extractants for immobilization, it can be more widely used in the market.

[0026] See also Figures 1 to 3 , Figure 1 The present invention is a flow chart of the method for preparing the solid-state extraction resin. Figure 2 The present invention is a detailed method flow chart of the method for preparing the solid-state extraction resin. As shown in the figure, the method for preparing the solid-state extraction resin 100 includes a resin cleaning stage (step S110), a solvent treatment stage (step S120) and a non-solvent treatment stage (step S130), and the resin cleaning stage (step S110) includes steps S11, S12, S13, S14 and S15, the solvent treatment stage (step S120) includes steps S21 and S22, and the non-solvent treatment stage (step S130) includes steps S31 and S32.

[0027] Further, the present invention is a method for preparing a solid-state extraction resin by using phase separation technology to efficiently fix a liquid extractant on a resin. The preparation method 100 of the solid-state extraction resin includes the following steps: preparing a resin, and preparing 4M hydrochloric acid and 12M methanol as a cleaning agent for cleaning the resin (step S11). It should be noted that the type of resin should be selected before the process of preparing the resin. The resin and the cleaning agent are added in a ratio of 1:3 (g:ml) (step S12). The resin is continuously contacted with the cleaning agent to obtain a cleaned resin (step S13). Hot water is used for washing several times, and the hydrochloric acid and methanol are washed (step S14); drying is performed at high temperature to obtain a dry resin (step S15). The dry resin is stirred with an organic alcohol of 30-80 vol% in a ratio of 1:50 (g:ml), thereby swelling the dry resin into a swollen resin (step S21). A metal extractant is added, and the metal extractant is fully contacted with the swollen resin in a homogeneous phase (step S22). Deionized water is used as a non-solvent. After step S22, deionized water is added until the aqueous solution becomes turbid (step S31) to produce phase separation. The organic alcohol and the metal extractant are allowed to undergo rapid phase separation, so that the metal extractant is fixed in the resin, thereby producing a solid extraction resin (step S32). It should be noted that in step S22, the solution composition range at this time is in a "homogeneous (clear)" region (such as Figure 3 As shown), in step S32, the solution composition range at this time is located in a "phase separation" region (such as Figure 3 In addition, the resin in step S11 is a porous resin, and the characteristics of the resin include a high molecular adsorbent polymerized with styrene as a monomer and other cross-linking agents.

[0028] In one embodiment of the present invention, the type of metal extractant can be acidic extractants, acidic chelating extractants, alkaline extractants or solvent extractants. Further, the metal extractant can be one of di(2-ethylhexyl)phosphoric acid (Di(2-ethylhexyl)phosphoric acid, abbreviated as D2EHPA), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (Mono-2-ethylhexyl(2-ethylhexyl)phosphonate, abbreviated as PC88A), and methyl tri-n-octyl ammonium chloride (Trioctyl methyl ammonium chloride, abbreviated as Aliquat336), and the present invention is not limited to any of the above. In the above step S22, before adding the metal extractant, a suitable metal extractant should be selected.

[0029] The resin used in the present invention is a porous resin, and the metal extractant can be selected according to the characteristics of the extract, so it has a wide range of applications. The following is a detailed description of each step. In the solvent treatment stage (step S120), the pre-treated dry resin is stirred with 30-80 vol% ethanol at a ratio of 1:50 (g:ml) for 10-60 minutes. This process can swell the resin, enlarge the pores, and loosen the resin molecular chains, which is conducive to the subsequent fixation of the extractant molecules. After the resin swells, add 0.15-1M of metal extractant and continue stirring for 1 hour. During the process, the solution composition needs to maintain a clear and transparent uniform phase. The appropriate solution composition range is as follows. Figure 3 The “clear” region of FIG.

[0030] In addition, in the non-solvent treatment stage (step S130), deionized water is used as a non-solvent, and an appropriate amount of deionized water is added to the resin impregnated with the metal extractant until the aqueous solution becomes turbid. At this time, the ethanol and the metal extractant undergo rapid phase separation, so that the extractant is fixed in the resin to obtain a solid extraction resin. The appropriate solution composition range for adding the non-solvent is as follows: Figure 3 The phase separation region is shown in FIG.

[0031] The present invention will be further described in detail with reference to the following examples. It should be understood that the examples are merely illustrative and should not be construed as limiting the implementation of the present invention.

[0032] Before proceeding with the following description, it should be understood that the following tests were performed on the following embodiments and comparative example 1:

[0033] 1. The content of metal extractant fixed in the resin: the content of metal extractant fixed (mmol·g -1 )=1000×(weight of dry solid extraction resin-weight of resin after pretreatment)÷molecular weight of extractant÷weight of resin after pretreatment. The sample was subjected to gravimetric analysis in an oven and dried at 60°C for one week before measurement.

[0034] 2. Stability test: stability (%) = weight of resin after shaking / weight of resin before shaking × 100%. The stability test is to shake the solid-state extraction resin in ultrasonic vibration for 30 minutes, and then compare the weight before and after the vibration. The percentage of the weight retained before the vibration to the weight retained after the vibration is the stability (%) of the solid-state extraction resin.

[0035] [Resin cleaning stage of the embodiment of the present invention]

[0036] A porous resin (hereinafter referred to as resin, manufacturer model: AMBERLITE XAD-4) was used, and 4M hydrochloric acid and 12M methanol were used as cleaning agents for cleaning the resin. The resin and the cleaning agent were added in a ratio of 1:3 (g:ml), and the resin and the cleaning agent were kept in contact for 12 hours to obtain a clean resin. The resin was then washed several times with 60°C hot water to wash away the hydrochloric acid and methanol, and then dried at 60°C for one week. The weight of the pre-treated resin was obtained by weighing.

[0037] [Solvent treatment stage of the embodiment of the present invention]

[0038] The metal extractant (to extract metal ions in water) used in the embodiment is Bis(2-ethylhexyl)phosphate. The pre-treated dry resin was stirred with 70 vol% ethanol at a ratio of 1:50 (g:ml) for 30 minutes to swell the resin, and then 0.15 M Bis(2-ethylhexyl)phosphate was added and stirred for 1 hour to allow the Bis(2-ethylhexyl)phosphate to fully contact the resin.

[0039] [Non-solvent treatment stage of the embodiment of the present invention]

[0040] In order to make the ethanol and metal extractant separate quickly in the solvent treated extract, deionized water was adjusted to more than 70% of the total solution. Figure 3As shown, the solution composition range is in the "phase separation" region, so that the extractant is fixed in the resin. The resin is then dried at 60°C for one week to obtain a solid extraction resin, which is weighed to obtain the weight of the solid extraction resin. The weight and the weight of the pre-treated resin are used to deduce the amount of the immobilized extractant.

[0041] [Stability test of the embodiment of the present invention]

[0042] After the solid extraction resin was placed in an ultrasonic oscillator for 30 minutes, the stability test showed that more than "97%" of the Bis(2-ethylhexyl)phosphate was retained in the resin, indicating good stability.

[0043] In order to highlight the efficacy of the method of the present invention, comparative examples were designed using resins prepared by solvent impregnation. Comparative Example 1 is a resin prepared by solvent impregnation (without solvent / non-solvent treatment step).

[0044] [Resin cleaning stage of Comparative Example 1]

[0045] 4M hydrochloric acid and 12M methanol were used as cleaning agents for cleaning the resin. The resin and the cleaning agent were added in a ratio of 1:3 (g:ml). The resin and the cleaning agent were kept in contact for 12 hours to obtain a clean resin. The resin was then washed several times with 60°C hot water to wash away the hydrochloric acid and methanol, and then dried at 60°C for one week.

[0046] [Solvent treatment stage of Comparative Example 1]

[0047] The pre-treated dry resin was stirred with 70 vol% ethanol at a ratio of 1:50 (g:ml) for 30 minutes to swell the resin, and then 0.15 M Bis(2-ethylhexyl)phosphate was added and stirred for 1 hour to allow the Bis(2-ethylhexyl)phosphate to fully contact the resin. After washing with water several times, the resin was dried at 60°C for one week and weighed to obtain the weight of the solid extraction resin.

[0048] [Stability test of comparative example 1]

[0049] After the solid extraction resin was placed in an ultrasonic oscillator for 30 minutes, the stability test showed that only "66.66%" of di-(2-ethylhexyl) phosphoric acid (Bis(2-ethylhexyl)phosphate) remained in the resin, indicating that the use of the solvent impregnation method (without the solvent / non-solvent treatment step) was not conducive to the fixation of the extractant.

[0050] The data of the embodiment of the present invention and the comparative example 1 are shown in the following Table 1:

[0051] Table 1

[0052]

[0053]

[0054] Table 1 is a summary of the embodiments of the present invention and Comparative Example 1. From the comparison, it can be seen that the resin that has undergone the solvent / non-solvent treatment step can immobilize more extractants, and the stability is much higher than that of the resin that has only undergone the solution treatment step.

[0055] In summary, the present invention can improve the content of resin-fixed extractant through the solvent / non-solvent treatment step, and has excellent stability. Moreover, compared with liquid extractant, solid extraction resin can achieve the effect of separating the extraction phase from the non-extraction phase more quickly, and can greatly reduce the difficulty of separating the oil phase from the water phase in the liquid extraction process.

[0056] In summary, the preparation method of the solid-state extraction resin disclosed in the present invention can achieve the following effects:

[0057] 1. The extraction effect can be improved by selecting different extractants according to different targets;

[0058] 2. It is fixed in the pores of the carrier, and the immobilized extractant has good stability in the carrier; and

[0059] 3. The solid-state extraction resin can still maintain its extraction effect after multiple extraction / regeneration cycles.

[0060] The above is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention. Therefore, all equivalent changes or modifications based on the features and spirit described in the scope of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A method for preparing a solid-state extraction resin, characterized in that: include: S11: preparing a resin, and preparing 4M hydrochloric acid and 12M methanol as a cleaning agent for cleaning the resin; S12: adding the resin and the cleaning agent in a ratio of 1:3 (g:ml); S13: continuously contacting the resin with the cleaning agent to obtain a cleaned resin; S14: Wash with hot water several times to remove hydrochloric acid and methanol; S15: drying at high temperature to obtain a dry resin; S21: stirring the dry resin and 30-80 vol% of an organic alcohol at a ratio of 1:50 (g:ml), thereby swelling the dry resin into a swollen resin; S22: adding a metal extractant so that the metal extractant is fully in contact with the swelling resin; S31: using deionized water as a non-solvent, adding deionized water after step S22 until the aqueous solution becomes turbid; and S32: allowing the organic alcohol and the metal extractant to undergo rapid phase separation, so that the metal extractant is fixed in the resin, thereby producing a solid extraction resin; Among them, step S11, step S12, step S13, step S14 and step S15 are resin cleaning stages, step S21 and step S22 are solvent treatment stages, step S31 and step S32 are non-solvent treatment stages, wherein in step S22, the solution composition range at this time is in the "homogeneous (clear)" area, wherein in step S32, the solution composition range at this time is in the "phase separation (separation)" area.

2. The method for preparing a solid-state extraction resin according to claim 1, characterized in that: The resin in step S11 is a porous resin.

3. The method for preparing the solid-state extraction resin according to claim 1, characterized in that: The resin in step S11 is characterized by being a polymer adsorbent polymerized with styrene as a monomer and other cross-linking agents.

4. The method for preparing a solid-state extraction resin according to claim 1, characterized in that: The organic alcohol is used as a swelling agent.

5. The method for preparing a solid-state extraction resin according to claim 1, characterized in that: The metal extractant is an acidic extractant, an acidic chelating extractant, an anionic extractant or a solvent extractant.

6. The method for preparing a solid-state extraction resin according to claim 1, characterized in that: The metal extractant is one of di(2-ethylhexyl)phosphoric acid, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, and methyl tri-n-octyl ammonium chloride.

7. The method for preparing a solid-state extraction resin according to claim 1, characterized in that: The fixed content of the metal extractant is 0.5-3 mmol / g.

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