KR20040055217A - A method for manufacturing extraction rosin for extraction and separation of an rare earth element - Google Patents
A method for manufacturing extraction rosin for extraction and separation of an rare earth element Download PDFInfo
- Publication number
- KR20040055217A KR20040055217A KR1020020081850A KR20020081850A KR20040055217A KR 20040055217 A KR20040055217 A KR 20040055217A KR 1020020081850 A KR1020020081850 A KR 1020020081850A KR 20020081850 A KR20020081850 A KR 20020081850A KR 20040055217 A KR20040055217 A KR 20040055217A
- Authority
- KR
- South Korea
- Prior art keywords
- rare earth
- weight
- extraction
- resin
- earth elements
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Geology (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
본 발명은 희토류 원소의 추출분리를 위한 추출수지의 제조방법에 관한 것으로서 이는 특히, 희토류 원소의 추출분리를 위해 스틸렌, 디비닐벤젠의 공중합체 형성과정중에 희토류 추출제인 비스디에틸헥실포스피닉산과 기공형성제인 톨루엔과 n-헵탄을 중합시켜 분말형태의 추출수지를 제조하는 구성으로 분리 정제공정이 간편하고, 반 영구적으로 재생할 수 있으며, 희토류 원소의 고순도 분리가 용이하여 생산성을 크게 향상시킬 수 있는 희토류 원소의 추출분리를 위한 추출수지의 제조방법에 관한 것이다.The present invention relates to a method for preparing an extraction resin for extracting and separating rare earth elements. In particular, the present invention relates to bisdiethylhexylphosphonic acid and pores, which are rare earth extracting agents, during the copolymerization process of styrene and divinylbenzene for extracting and separating rare earth elements. It is a composition that prepares powder extract resin by polymerizing toluene and n-heptane as a forming agent, and is easy to separate and refine the process, semi permanently regenerated, and easy to separate high purity of rare earth elements. The present invention relates to a method for producing an extract resin for extracting and separating elements.
일반적으로 희토류 원소들은 물리적, 화학적 특성이 유사하고, 착물 킬레이트의 안정도 상수 차이가 크지 않기 때문에 현재는 이들을 주성분으로 함유하고 있는 광석을 산 또는 알카리로 분해하여 1차 추출물을 얻은 후, 이를 다시 분리정제하여 고순도 희토류 금속 및 화합물을 제조하고 있지만 분리정제 공정이 복잡하고 희토류 한 원소만을 분리하는 것이 매우 어려운 실정이다.In general, rare earth elements have similar physical and chemical properties, and the difference in stability constants of complex chelates is not large. Currently, ore containing them as a main component is decomposed with acid or alkali to obtain a primary extract, and then purified again. Although high purity rare earth metals and compounds are manufactured, the separation and purification process is complicated and it is very difficult to separate only rare earth elements.
그리고, 추출수지는, 레버트렐 레진(Levertrel Resin)으로 알려진스틸렌(styrene), 디비닐벤젠(Divinyl benzene)의 고분자 물질의 골격구멍(frame pore)에 추출제를 첨가하여 제조하고 있으나, 희토류 원소 분리의 경우 분리성능이 좋지 않은 단점이 있다.In addition, the extraction resin is prepared by adding an extractant to a frame pore of high molecular materials of styrene and divinyl benzene, which are known as levertrel resin, but are separated from rare earth elements. In the case of separation performance has a disadvantage.
이를 개선하기 위한 본 발명의 목적은, 분리 정제공정이 간편하게 이루어 지도록 하고, 반 영구적으로 재생할 수 있도록 하며, 희토류 원소의 고순도 분리가 용이하도록 하여 생산성을 크게 향상시킬 수 있도록 하고, 분리성능을 향상 시킬수 있도록 하는 희토류 원소의 추출분리를 위한 추출수지의 제조방법을 제공하는데 있다.An object of the present invention for improving this, to facilitate the separation and purification process, to be semi-permanent regeneration, to facilitate the high-purity separation of rare earth elements, to greatly improve the productivity, and to improve the separation performance The present invention provides a method for preparing an extract resin for extracting and separating rare earth elements.
도1은 본 발명에 따른 희토류 원소의 추출분리를 위함 추출수지의 제조방법을 도시한 순서도.1 is a flow chart illustrating a method of preparing an extract resin for extracting and separating rare earth elements according to the present invention.
도2는 본 발명에 제조방법중 톨루엔/n-헵탄을 첨가하지 않은 추출수지의 분리성능을 나타낸 그래프도.Figure 2 is a graph showing the separation performance of the extract resin not added toluene / n-heptane in the production method in the present invention.
도3a는 본 발명에 의한 제조방법중 톨루엔/n-헵탄을 5.5/0.5 중량%첨가한 추출수지의 분리성능을 도시한 그래프도.Figure 3a is a graph showing the separation performance of the extract resin added to the toluene / n-heptane 5.5 / 0.5% by weight in the production method according to the present invention.
도3b는 본 발명에 의한 제조방법중 톨루엔/n-헵탄을 5.5/2.5 중량%첨가한 추출수지의 분리성능을 도시한 그래프도.Figure 3b is a graph showing the separation performance of the extract resin added to the toluene / n-heptane 5.5 / 2.5% by weight in the production method according to the present invention.
도3c는 본 발명에 의한 제조방법중 톨루엔/n-헵탄을 5.5/5.5 중량%첨가한 추출수지의 분리성능을 도시한 그래프도.Figure 3c is a graph showing the separation performance of the extract resin added 5.5 to 5.5% by weight of toluene / n-heptane in the production method according to the present invention.
도3d는 본 발명에 의한 제조방법중 톨루엔/n-헵탄을 10/10 중량%첨가한 추출수지의 분리성능을 도시한 그래프도.Figure 3d is a graph showing the separation performance of the extract resin added 10/10% by weight of toluene / n-heptane in the production method according to the present invention.
도4a는 본 발명에 의한 제조방법중 pH 1의 조건으로 분리실험한 추출수지의 분리성능을 도시한 그래프도.Figure 4a is a graph showing the separation performance of the extraction resin separated under the conditions of pH 1 of the production method according to the present invention.
도4b는 본 발명에 의한 제조방법중 pH 2.5의 조건으로 분리실험한 추출수지의 분리성능을 도시한 그래프도.Figure 4b is a graph showing the separation performance of the extraction resin separated under the conditions of pH 2.5 of the production method according to the present invention.
도4c는 본 발명에 의한 제조방법중 pH 4의 조건으로 분리실험한 추출수지의 분리성능을 도시한 그래프도.Figure 4c is a graph showing the separation performance of the extraction resin separated under the conditions of pH 4 of the manufacturing method according to the present invention.
상기 목적들을 달성하기 위해 본 발명은, 스틸렌과 디비닐벤젠의 혼합물에 벤조일퍼록사이드를 첨가하여 공중합체를 만드는 과정에서 희토류 추출을 위한 추출제, 분산제, 안정제, 기공형성제를 첨가한후 교반속도 및 반응온도를 조절함으로서 희토류 원소를 고순도로 분리하는 희토류 원소의 추출분리를 위한 추출수지의 제조방법이 제공된다.In order to achieve the above object, the present invention, in the process of making a copolymer by adding benzoyl peroxide to the mixture of styrene and divinylbenzene, the stirring rate after adding the extractant, dispersant, stabilizer, pore-forming agent for rare earth extraction And a method for producing an extraction resin for extracting and separating rare earth elements which separates rare earth elements with high purity by controlling the reaction temperature.
이하, 첨부된 도면에 의거하여 본 발명의 실시예를 상세하게 설명하면 다음과 같다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
도1에서와 같이 본 발명은, 추출크로마토그래피법을 이용하며, 상기 추출크로마토그래피법은, 희토류 원소의 추출분리를 위한 추출수지를 제조함에 있어 고분자 공중합체에 희토류 추출제, 안정제, 분산제, 기공형성제를 첨가하여 고순도의희토류 원소를 추출하는데 사용하며, 영구적으로 재생하여 사용할 수 있는 추출수지의 합성방법이다.As shown in FIG. 1, the present invention uses an extraction chromatography method, and the extraction chromatography method is a rare earth extractant, stabilizer, dispersant, and pores in a polymer copolymer in preparing an extraction resin for extracting and separating rare earth elements. It is used to extract high purity rare earth elements by adding a forming agent, and it is a synthesis method of extract resin that can be recycled and used permanently.
즉, 스틸렌(Styrene)과 디비닐벤젠(divinyl benzene)의 혼합물에 벤조일퍼록사이드(Benzoyl peroxide) 또는 아조비스이소부틸로니트릴 (Azobisisobutyronitrile)를 첨가하여 공중합체를 만드는 과정에서 희토류 추출을 위한 추출제로 비스디에틸헥실포스피닉산 (bisethylhexyl Phosphinic acid), 분산제로 제이옥탄산(bis octanoic acid), 안정제로 메틸셀룰로우즈(methyl cellulose), 기공형성제로 톨루엔(Toluene)과 n-헵탄(Heptane)의 혼합물을 첨가하고 교반속도 및 반응온도를 조절함으로서 희토류 원소를 고순도로 분리한다.In other words, benzoyl peroxide or azobisisobutyronitrile was added to a mixture of styrene and divinyl benzene to extract rare earth as an extractant for rare earth extraction. A mixture of diethylhexyl Phosphinic acid, bis octanoic acid as a dispersant, methyl cellulose as a stabilizer, toluene and n-heptane as a pore forming agent The rare earth element is separated into high purity by adding and controlling the stirring speed and reaction temperature.
그리고, 상기 희토류 원소를 냉각및 분리하고, 이를 알코올로 세척한후 건조시켜 추출수지를 제조한다.Then, the rare earth element is cooled and separated, washed with alcohol and dried to prepare an extract resin.
상기와 같은 제조방법을 실시예를 들어 구체적으로 설명한다.The manufacturing method as described above will be described in detail with reference to Examples.
<실시예1>Example 1
증류수 20∼70 중량%와, 스틸렌 4∼20 중량%, 그리고 함량이 50%인 디비닐벤젠을 0.5∼10 중량%, 개시제로 과산화벤조일 또는 아조비스이소부틸로니트릴 0.05∼0.5 중량%의 혼합물에 기공형성제 톨루엔 1∼30 중량%와 n-헵탄 1∼30 중량%를 첨가한 다음 70∼90℃ 에서 400∼2000rpm으로 교반반응을 실시한다.To a mixture of 20 to 70% by weight of distilled water, 4 to 20% by weight of styrene and 50% to 100% of divinylbenzene, and 0.05 to 0.5% by weight of benzoyl peroxide or azobisisobutylonitrile as an initiator 1 to 30% by weight of the pore-forming agent toluene and 1 to 30% by weight of n-heptane were added, followed by stirring at 400 to 2000 rpm at 70 to 90 ° C.
여기에, 희토류의 추출을 위한 추출제로 비스디에틸헥실포스피닉산을 5∼20 중량%첨가하고, 분산제로서 제이옥탄산을 3∼10 중량%를 첨가하며, 안정제로서 1∼5% 메틸셀룰로우즈 수용액을 4∼10 중량%를 첨가한 후 3∼5시간 교반반응을 시킨다.To this, 5-20% by weight of bisdiethylhexylphosphonic acid is added as an extractant for extracting rare earths, 3-10% by weight of dioctanoic acid is added as a dispersant, and 1-5% methylcellulose is used as a stabilizer. 4-10 wt% of the Woods aqueous solution is added, followed by stirring for 3 to 5 hours.
그리고, 교반반응의 종료후 70∼90℃의 온도에서 12∼24시간 동안 반응을 시킨 다음 냉각하고, 상기 추출수지를 걸러내서 알코올로 10∼60분 동안 세척하는 작업을 수행한다.After the completion of the stirring reaction, the reaction is carried out at a temperature of 70 to 90 ° C. for 12 to 24 hours, followed by cooling. The extract is filtered and washed with alcohol for 10 to 60 minutes.
한편, 분산제로는 제이옥탄산, 케로신(kerosene), 카프릭 산(Caprylic acid)을 사용할 수 있으며, 안정제는 1∼5% 메틸셀룰로우즈 수용액 대신 3∼10% 아라빅 고무(arabic gum) 수용액으로 대체하여 사용할 수 있다.On the other hand, as the dispersant may be used zeokanoic acid, kerosene (kerosene), capric acid (caprylic acid), stabilizer 3-10% arabic gum (instead of 1-5% aqueous solution of methylcellulose) It can be used as an aqueous solution.
또한, 기공형성제는 톨루엔 대신 시클로헥산(Cyclohexane), 벤젠(benzene), 에틸벤젠(Ethyl benzene)을 사용할 수 있으며, n-헵탄 대신 페놀(phenol), 아세톤(Aceton), 아세트산(Acetic Acid)을 사용할 수 있다.In addition, the pore-forming agent may use cyclohexane, benzene, ethyl benzene instead of toluene, and phenol, acetone, acetic acid instead of n-heptane. Can be used.
이와 같이 제조된 추출수지는, 기공형성제의 첨가량이 많아 질수록 분리성능이 우수하였다.The extraction resin thus prepared was excellent in separation performance as the amount of pore-forming agent added increased.
다음은, 상기와 같은 방법으로 이루어진 본 발명을 추출수지 제조방법을 보다 구체화하여 설명한다.Next, the present invention made by the above-described method will be described in more detail the extraction resin manufacturing method.
(1)추출수지의 희토류 원소에 대한 수착성능 평가 (1) Evaluation of Sorption Performance on Rare Earth Elements of Extraction Resin
희토류 원소의 추출분리를 위하여 위의 실험방법으로 도2및 도3에서와 같이 기공형성제인 톨루엔/n-헵탄을 첨가하지 않은 추출수지와 5.5/0.5, 5.5/2.5, 5.5/5.5, 10/10 중량%로 첨가하여 추출수지를 제조하였으며, 희토류 원소에 대한 수착성능의 평가를 위하여 다음과 같은 실험과정을 거쳐 측정하였다.In order to extract and separate rare earth elements, as shown in Figs. Extraction resin was prepared by adding in weight%, and was measured through the following experimental procedure for evaluation of sorption performance on rare earth elements.
추출수지는 증류수에 충분히 세척한 후, 60℃의 오븐에서 24시간 건조하였고,추출수지는 정확히 0.2g 취하여 40ml 시료병에 넝은후 20mg/ml의 농도를 갖는 희토류 흡착용액(산화가돌륨, 산화테르븀) 2ml와 농도가 조절된 염산용액 18ml를 혼합하여 수지와 함께 플라스크에 넣어 5분간 수지를 팽윤(swelling)시켰다.The extracted resin was sufficiently washed in distilled water and then dried in an oven at 60 ° C. for 24 hours. The extracted resin was precisely taken in 0.2 g, poured into a 40 ml sample bottle, and had a rare earth adsorption solution having a concentration of 20 mg / ml. 2 ml of terbium) and 18 ml of hydrochloric acid with a controlled concentration were mixed, and the resin was swelled for 5 minutes in a flask with the resin.
이렇게 준비된 플라스크를 30℃ 항온기내의 진탕기에 삽입하여 100rpm 으로 24시간 흔들어 준다.The flask thus prepared is inserted into a shaker in a 30 ° C thermostat and shaken at 100 rpm for 24 hours.
그리고, 추출수지가 희토류 이온과 흡착평형이 이루어진 후 추출수지를 여과하고, 여과액 중에 흡착되지 않은 희토류 금속을 정량하여 다음 식에 따라 분배계수(Kd)값을 계산하였으며, 그 결과를 표1, 표2에서 희토류 용액 수착도에 따른 분배계수로서 나타내었다.After the extraction resin had an adsorption equilibrium with the rare earth ions, the extraction resin was filtered, the rare earth metal not adsorbed in the filtrate was quantified, and the partition coefficient (Kd) value was calculated according to the following equation. Table 2 shows the partition coefficient according to the rare earth solution sorption degree.
즉, 표1, 2의 결과에서 알수 있듯이 제조된 추출수지는, 톨루엔과 n-헵탄의 첨가량에 상관없이 희토류 원소의 수착능이 우수하였다.In other words, as can be seen from the results of Tables 1 and 2, the produced extraction resin was excellent in the sorption capacity of the rare earth element regardless of the addition amount of toluene and n-heptane.
(2)추출수지의 희토류 원소에 대한 분리성능 평가 (2) Evaluation of Separation Performance of Rare Earth Elements in Extraction Resin
상기와 같이 제조된 추출수지의 분리성능을 평가하기 위해 직경이 20cm, 내경이 1cm의 컬럼을 사용하고, 추출수지는 1∼1.5mol/ℓ 의 염산용액에 4∼6시간 교반없이 팽윤시킨 후, 교반에 의해 부유하는 미세입자 및 불순물을 제거한 다음 기포가 생기지 않도록 컬럼에 15cm 충진한다.In order to evaluate the separation performance of the extraction resin prepared as described above, using a column having a diameter of 20 cm and an inner diameter of 1 cm, the extraction resin swelled in 1 ~ 1.5 mol / L hydrochloric acid solution without stirring for 4 to 6 hours, Floating fine particles and impurities are removed by stirring, and the column is filled with 15 cm to prevent bubbles from forming.
여기에, 농도 50g/ℓ 로 제조된 희토류 혼합용액(산화가돌리늄:산화테르븀=1:1) 1.5ml를 주입하여 추출수지에 흡착시킨 후, 염산용액은 0.1∼0.5mol/ℓ로 투입하여 분리실험을 실시하고, ICP-AES로 용출액을 분석하였다.Then, 1.5 ml of a rare earth mixed solution (gadolinium oxide: terbium oxide = 1: 1) prepared at a concentration of 50 g / l was injected and adsorbed onto the extraction resin, and then a hydrochloric acid solution was added at a concentration of 0.1 to 0.5 mol / l. The eluate was analyzed by ICP-AES.
이때, 분리성능은 크로마토그래피에서 분리효율 척도로 이용되는 아래 식을 사용하였다.At this time, the separation performance was used the following equation used as a separation efficiency measure in chromatography.
tA: 용질 A의 크로마토그래피 peak 위치t A : Chromatographic peak position of solute A
tB: 용질 B의 크로마토그래피 peak 위치t B : Chromatographic peak position of solute B
그 결과, 기공형성제인 톨루엔/n-헵탄의 첨가량의 변화에 따른 분리성능은, 표3및 이와 관련된 도2및 도3에서와 같이, 희토류 원소를 분리할 때 희토류 원소의 분리성능( GdTb)를 나타낸 것으로서 톨루엔/n-헵탄이 첨가되지 않은 추출수지는 희토류 원소의 분리가 거의 이루어지지 않았으며, 톨루엔/n-헵탄이 5.5/0.5 중량%일때 분리성능은 0.28이고, 5.5/2.5 중량%일 때 분리성능은 0.33이다.As a result, the separation performance according to the change in the addition amount of toluene / n-heptane as a pore-forming agent, the separation performance of the rare earth elements (Gd Tb ) when separating the rare earth elements, as shown in Table 3 and related Figures 2 and 3 As the toluene / n-heptane-extracted extract resin was rarely separated from rare earth elements, the separation performance was 0.28 and 5.5 / 2.5 wt% when the toluene / n-heptane was 5.5 / 0.5 wt%. The separation performance is 0.33.
또한, 톨루엔/n-헵탄이 5.5/5.5 중량%일 때는 분리성능이 0.35이며, 10/10 중량%로 첨가하였을 때는 분리도가 0.73으로 기공형성제의 첨가량이 많이 첨가될수록 추출수지의 분리성능이 우수한 것을 알 수 있다.In addition, when toluene / n-heptane was 5.5 / 5.5 wt%, the separation performance was 0.35, and when it was added at 10/10 wt%, the separation was 0.73. It can be seen that.
(3)pH변화에 따른 추출수지의 희토류 원소 분리성능 평가 (3) Evaluation of Rare Earth Element Separation Performance of Extraction Resin According to pH Change
상기에서 설명한 바와같이, 분리성능 평가를 하였을 때 기공형성제인 톨루엔/n-헵탄을 10/10 중량%첨가하여 제조한 추출수지가 분리성능이 우수함을 확인하였으며, 톨루엔/n-헵탄을 10/10 중량%첨가하여 제조한 추출수지로 pH변화에 따른 추출수지의 희토류 원소 분리성능 평가 실험을 하여 그 결과를 표4및 이와 관련된 도4에 도시하였다.As described above, when the separation performance was evaluated, it was confirmed that the extraction resin prepared by adding 10/10% by weight of toluene / n-heptane as a pore-forming agent showed excellent separation performance, and 10/10 of toluene / n-heptane. The extraction performance of the rare earth element of the extraction resin according to the pH change with the extraction resin prepared by the addition of weight% was carried out and the results are shown in Table 4 and FIG. 4.
이때, 추출수지는 여러차례 분리실험 시 재생이 가능한 가를 알아보기 위해컬럼내 한번 충진된 추출수지로 반복실험을 하였다.At this time, the extraction resin was repeated experiment with the extraction resin once filled in the column to determine whether it can be regenerated in several separate experiments.
이 결과, pH 1일 때는 분리도가 0.60이고, pH 2.5일 때는 분리도가 0.73이며, pH 4일때는 분리도가 0.89이다.As a result, at pH 1, the degree of separation is 0.60, at pH 2.5, the degree of separation is 0.73, and at pH 4, the degree of separation is 0.89.
즉, 추출수지의 pH가 높을수록 희토류 원소의 분리성능이 우수한 것을 알수있다.In other words, the higher the pH of the extraction resin, the better the separation performance of rare earth elements.
이와 같이 본 발명에 의하면, 분리 정제공정이 간편하게 이루어 지고, 반 영구적으로 재생할 수 있으며, 희토류 원소의 고순도 분리가 용이하도록 하여 생산성을 크게 향상시키고, 분리공정을 단축시켜 성능을 향상 시킴으로써 생산성을 향상시키는 효과가 있는 것이다.Thus, according to the present invention, the separation and purification process is made simple, can be semi-permanently regenerated, to facilitate the high-purity separation of rare earth elements, greatly improve the productivity, shorten the separation process to improve the performance by improving the productivity It works.
본 발명은 특정한 실시예에 관련하여 도시하고 설명 하였지만, 이하의 특허청구범위에 의해 제공되는 본 발명의 정신이나 분야를 벗어나지 않는 한도내에서본 발명이 다양하게 개량 및 변화될수 있다는 것을 당업계에서 통상의 지식을 가진자는 용이하게 알수 있음을 밝혀 두고자 한다.While the invention has been shown and described with respect to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the invention as provided by the following claims. I would like to clarify that those who have knowledge of this can easily know.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2002-0081850A KR100500730B1 (en) | 2002-12-20 | 2002-12-20 | A method for manufacturing extraction rosin for extraction and separation of an rare earth element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2002-0081850A KR100500730B1 (en) | 2002-12-20 | 2002-12-20 | A method for manufacturing extraction rosin for extraction and separation of an rare earth element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20040055217A true KR20040055217A (en) | 2004-06-26 |
| KR100500730B1 KR100500730B1 (en) | 2005-07-12 |
Family
ID=37347932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR10-2002-0081850A KR100500730B1 (en) | 2002-12-20 | 2002-12-20 | A method for manufacturing extraction rosin for extraction and separation of an rare earth element |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100500730B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141395A (en) * | 2017-06-27 | 2017-09-08 | 白才蓉 | It is a kind of for extracting resin of heavy metal-containing wastewater treatment and preparation method thereof |
| CN109320671A (en) * | 2018-09-12 | 2019-02-12 | 辽宁大学 | The preparation of epoxy acrylic extration resin and its application in extracted germanium |
| RU2693714C1 (en) * | 2018-12-25 | 2019-07-04 | Общество С Ограниченной Ответственностью "Лаборатория Инновационных Технологий" | Method of extraction separation of rare-earth elements |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101640240B1 (en) | 2014-05-20 | 2016-07-15 | 한국광해관리공단 | System and method for purifying rare earth mine drainage |
-
2002
- 2002-12-20 KR KR10-2002-0081850A patent/KR100500730B1/en active IP Right Grant
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141395A (en) * | 2017-06-27 | 2017-09-08 | 白才蓉 | It is a kind of for extracting resin of heavy metal-containing wastewater treatment and preparation method thereof |
| CN109320671A (en) * | 2018-09-12 | 2019-02-12 | 辽宁大学 | The preparation of epoxy acrylic extration resin and its application in extracted germanium |
| CN109320671B (en) * | 2018-09-12 | 2021-01-08 | 辽宁大学 | Preparation of epoxy acrylic acid extraction resin and application of epoxy acrylic acid extraction resin in germanium extraction |
| RU2693714C1 (en) * | 2018-12-25 | 2019-07-04 | Общество С Ограниченной Ответственностью "Лаборатория Инновационных Технологий" | Method of extraction separation of rare-earth elements |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100500730B1 (en) | 2005-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4599175A (en) | Process for separating and purifying metallic elements by displacement chromatography | |
| US4631177A (en) | Method for recovering gallium | |
| CN107501045B (en) | Method for separating and purifying butanetriol from fermentation liquor by using macroporous adsorption resin | |
| JP2003304812A (en) | Beverage feeder having function to remove purine alkaloid | |
| KR100500730B1 (en) | A method for manufacturing extraction rosin for extraction and separation of an rare earth element | |
| US8062526B2 (en) | Separation of platinum group metals | |
| CN102728096B (en) | Edulcoration method of ginkgo leaf extraction process | |
| CN111205297A (en) | Preparation method of forbitasvir RRRR type enantiomer | |
| Yasuda et al. | Separation of germanium from ethylene glycol distillates by N-methylglucamine resin | |
| CN110331303B (en) | Method for continuously extracting and separating medium-heavy rare earth chloride solution | |
| JPS5845341A (en) | Separation of rare earth metal | |
| US3970605A (en) | Method for recovering vinyl sulfonate monomers | |
| CA1192187A (en) | Selective removal of sulfonic resin extractables with acrylic anion exchange resins | |
| JPH084694B2 (en) | Method for reducing pores in beverage filter media | |
| US4105701A (en) | Purification of materials containing carbonyl contaminants | |
| CN111205298A (en) | Preparation method of forbitasvir RRRS type isomer | |
| CN109675532B (en) | Hydrophilic porous polyvinyl alcohol resin and preparation method and application thereof | |
| Juang et al. | Column sorption of divalent metals from sulfate solutions by extractant‐impregnated macroporous resins | |
| KR20090094528A (en) | Synthesis Method of Extraction Resin for Separaton of Rare Earth Elements | |
| CN116065021B (en) | Ion exchange separation and purification method of single rare earth element samarium | |
| US4250155A (en) | Method of purifying phosphoric acid after solvent extraction | |
| CN110420480B (en) | Method for removing ammonium alkyl benzene sulfonate from carbonate precipitant for rare earth | |
| CN116873966A (en) | Method for refining 5N-level scandium oxide by column chromatography | |
| CN108854155B (en) | Selective magnetic solid phase extraction method of green tea polyphenol | |
| JP3963531B2 (en) | Method for producing column packing material for optical isomer separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20130628 Year of fee payment: 9 |
|
| FPAY | Annual fee payment |
Payment date: 20140630 Year of fee payment: 10 |
|
| FPAY | Annual fee payment |
Payment date: 20150619 Year of fee payment: 11 |
|
| FPAY | Annual fee payment |
Payment date: 20160629 Year of fee payment: 12 |
|
| FPAY | Annual fee payment |
Payment date: 20170626 Year of fee payment: 13 |
|
| FPAY | Annual fee payment |
Payment date: 20180625 Year of fee payment: 14 |
|
| FPAY | Annual fee payment |
Payment date: 20190626 Year of fee payment: 15 |