KR100608254B1 - The preparation method of dithiadecamethylene tetramine adsorbent for precious metals - Google Patents
The preparation method of dithiadecamethylene tetramine adsorbent for precious metals Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains three hetero rings
- C07D513/18—Bridged systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
Abstract
본 발명은 디티아데카메틸렌 테트라민 흡착제의 제조방법에 관한 것으로, 20℃ 이하의 온도에서 에틸렌디아민과 포름알데히드를 1: 3의 몰비로 반응시킨 다음, 황화 수소와 반응시키는 것으로 구성된다. The present invention relates to a process for preparing thiatia decamethylene tetramine adsorbent, comprising reacting ethylenediamine and formaldehyde in a molar ratio of 1: 3 at a temperature of 20 ° C. or lower, followed by reaction with hydrogen sulfide.
귀금속, 흡착제, 디티아데카메틸렌 테트라민Precious Metals, Adsorbents, Dithiadecamethylene Tetramine
Description
본 발명은 귀금속 흡착제로 사용되는 디티아데카메틸렌 테트라민 흡착제의 제조방법에 관한 것으로, 상세하게는 여러가지 금속 이온이 혼합되어 있는 용액으로부터 금, 은, 백금 및 백금족 금속과 같은 귀금속 이온을 흡착 추출하는데 사용되는 디티아데카메틸렌 테트라민 흡착제의 제조방법에 관한 것이다.The present invention relates to a process for preparing thiadecamethylene tetramine adsorbents used as noble metal adsorbents. Specifically, the present invention relates to adsorption extraction of precious metal ions such as gold, silver, platinum and platinum group metals from a solution containing various metal ions. The manufacturing method of the dithiadecamethylene tetramine adsorbent used is related.
종래, 일반적으로 사용되어 왔던 귀금속 흡착제(상품명 : SRAFION NMRR)는 노란색을 띄고 있으며 스티렌과 디비닐벤졸(2%)의 공중합체로서, 이소티오우레아 그룹을 포함하고 있다. 이 흡착제는 백금족 금속에 대한 선택성을 나타낸다. 0.05M HCl 용액중에서의 흡착능은 다음과 같다(g/g) : Pt-0.488, Pd-0.218, Rh-0.190 및 Ir-0.158[A sorption concentrating platinum metals and gold in flowing systems of the analysis. L.V.Bagachyova, I.A.Kovalyov, etc 17 International Cheenyatv meeting in chemistry, the analysis and technologues of platinum metals, Moscow, on April 17-19, 2001 ]. Conventionally, the noble metal adsorbent (trade name: SRAFION NMRR), which has been generally used, is yellow and has a isothiourea group as a copolymer of styrene and divinylbenzol (2%). This adsorbent exhibits selectivity for platinum group metals. Adsorption capacity in 0.05M HCl solution is as follows (g / g): Pt-0.488, Pd-0.218, Rh-0.190 and Ir-0.158 [A sorption concentrating platinum metals and gold in flowing systems of the analysis. L.V.Bagachyova, I.A.Kovalyov, etc 17 International Cheenyatv meeting in chemistry, the analysis and technologues of platinum metals, Moscow, on April 17-19, 2001].
그러나, 종래의 흡착제를 사용한 이 추출방법은 흡착 후에 흡착제를 소각시키는데 상당한 부하가 있다는 치명적인 결합이 있었다. 다량의 흡착제 소각에는 많은 에너지 소모가 필요한데, 실제 전기로 소각시 870℃ 이상의 고온이 필요하다. However, this extraction method using conventional adsorbents has a lethal bond that there is a significant load on incineration of adsorbents after adsorption. Incineration of a large amount of adsorbent requires a lot of energy, and incineration of an electric furnace requires a high temperature of 870 ° C or higher.
따라서, 본 발명자는 비교적 저온에서 소각이 가능하여 에너지를 절감시킬 수 있고, 귀금속에 대한 선택성과 흡착능이 우수하면서, 특히 산이나 알칼리 용액 등 액성에 관계없이 흡착능이 우수한 귀금속 흡착제로서 디티아데카메틸렌 테트라민 흡착제를 개발하여 특허출원한 바 있다.Therefore, the present inventors can incinerate at a relatively low temperature, thereby saving energy, and excellent in selectivity and adsorption capacity for noble metals, and in particular, thiatia decamethylene tetra as a noble metal adsorbent having excellent adsorption capacity regardless of liquidity such as acid or alkaline solution. The patent application was developed by developing a civil adsorbent.
그러나, 종래의 문헌에서는 디티아데카메틸렌 테트라민(S2N4(CH2)10 ) 흡착제의 제조방법에 대해 게시한 바가 없으며, Goerge Walker "Formaldehyde", the USSR, Moscow, the State chemical publishing house, 1957에서는 4몰의 포름알데히드와 2몰의 에틸렌디아민을 축합하여 N4(CH2)8을 제조하는 방법에 대해서만 게시되어 있다. 또, 러시아 특허 제 2160232 C1(1999.7.14) 호에서는 분자식은 동일하나 다른 구조의 화합물이 생성되었다. 이 구조식의 화합물은 활성 중심인 히드록실 그룹( OH-)이 없어서 일반적인 온도와 압력에서 약산인 황화수소(H2S)에 반응할 수 없다. However, there is no publication in the prior art about the preparation of dithiadecamethylene tetramine (S 2 N 4 (CH 2 ) 10 ) adsorbent, Goerge Walker "Formaldehyde", the USSR, Moscow, the State chemical publishing house , 1957 discloses only a method for producing N 4 (CH 2 ) 8 by condensing 4 moles of formaldehyde and 2 moles of ethylenediamine. In Russian Patent No. 2160232 C1 (1999.7.14), compounds having the same molecular formula but different structures were produced. The compounds of the structural formula is a hydroxyl group (OH -) active center can not respond to hydrogen sulfide (H 2 S) is a weak acid because under normal temperature and pressure.
포름알데히드 수용액의 상태에 대한 연구 결과로부터, 알데히드 수용액은 메틸렌 글리콜의 일수화물 CH2-(OH)2, 수화된 저분자량 중합체 또는 일반식 HO-(CH2O)H의 폴리옥시메틸렌 글리콜의 평형 혼합물을 형성한다는 것을 알 수 있다. 평형의 조건은 온도와 용액 중의 포름알데히드의 함량에 의존한다. Goerge Walker "Formaldehyde", the USSR, Moscow, the State chemical publishing house, 1957의 연구결과에서, 포름알데히드 30% 농도, 20℃, pH=2.6-4.5에서 평형반응은 다음과 같다:From the study of the state of aqueous formaldehyde solution, the aqueous aldehyde solution is the equilibrium of monohydrate CH 2- (OH) 2 of methylene glycol, hydrated low molecular weight polymer or polyoxymethylene glycol of general formula HO- (CH 2 O) H. It can be seen that it forms a mixture. The condition of equilibrium depends on the temperature and the content of formaldehyde in the solution. In a study by Goerge Walker "Formaldehyde", the USSR, Moscow, the State chemical publishing house, 1957, the equilibrium reaction at 30% formaldehyde concentration, 20 ° C, pH = 2.6-4.5 is as follows:
HOCH2OCH2OCH2OH ↔ CH2 +OCH2OCH2 O- + H+ + OH- HOCH 2 OCH 2 OCH 2 OH ↔ CH 2 + OCH 2 OCH 2 O - + H + + OH -
따라서, 본 발명의 목적은 포름알데히드와 에틸렌디아민의 반응조건을 적절히 조절하여 N4(CH2)10(OH)4를 제조한 다음, 황화수소와 반응시켜 디티아데카메틸렌 테트라민(S2N4(CH2)10) 흡착제를 제조하는 방법을 제공하는 것이다.
Accordingly, an object of the present invention is to prepare N 4 (CH 2 ) 10 (OH) 4 by appropriately adjusting the reaction conditions of formaldehyde and ethylenediamine, and then reacted with hydrogen sulfide to dithiadecamethylene tetramine (S 2 N 4 (CH 2 ) 10 ) to provide a method for producing the adsorbent.
상기 본 발명의 목적은 20℃ 이하의 온도에서 에틸렌디아민과 포름알데히드를 1: 3의 몰비로 반응시킨 다음, 황화 수소와 반응시키는 것으로 구성되는 디티아데카메틸렌 테트라민의 제조방법에 의해 달성된다. The object of the present invention is achieved by a process for producing dithiadecamethylene tetramine consisting of reacting ethylenediamine with formaldehyde in a molar ratio of 1: 3 at a temperature of 20 ° C. or lower and then with hydrogen sulfide.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
1) 우선 에틸렌 디아민과 포름알데히드를 축합반응시킨다. 반응은 20℃ 이하에서 수행된다. 얼음에 의해 냉각된 용기에서 포름알데히드의 35% 수용액 H(CH2O)3OH에 에틸렌디아민 NH2(CH2)2NH2 을 서서히 부가한다. NH2(CH2)2NH2 : CH2O의 몰비는 1: 3이다. 포름알데히드에 대해 에틸렌디아민을 부가하면 초기에 반응은 다음과 같이 진행된다. 1) First, condensation reaction of ethylene diamine and formaldehyde is carried out. The reaction is carried out at 20 ° C. or lower. Ethylenediamine NH 2 (CH 2 ) 2 NH 2 is slowly added to a 35% aqueous solution H (CH 2 O) 3 OH of formaldehyde in a vessel cooled by ice. The molar ratio of NH 2 (CH 2 ) 2 NH 2 : CH 2 O is 1: 3. When ethylenediamine is added to formaldehyde, the reaction proceeds initially as follows.
에틸렌디아민이 더 부가되면 다음의 반응이 진행된다. If ethylenediamine is further added, the following reaction proceeds.
2) 에틸렌디아민과 포름알데히드의 반응이 종료되면, 황화수소를 부가하여 반응시켜 디티아데카메틸렌 테트라민 S2C10H20N4을 제조한다. 2) When the reaction between ethylenediamine and formaldehyde is completed, hydrogen sulfide is added to react to prepare dithiadecamethylene tetramine S 2 C 10 H 20 N 4 .
본 발명의 제조방법에 의해 제조된 디티아데카메틸렌 테트라민 흡착제는 강산이나 강알칼리에서도 안정하며, 분해되지 않는다. 1g의 흡착제로 약 0.6g의 귀금속을 흡착할 수 있다. The dithiadecamethylene tetramine adsorbent produced by the production method of the present invention is stable even in strong acid and strong alkali, and does not decompose. One gram of adsorbent can adsorb about 0.6 grams of precious metal.
실시예 1Example 1
얼음에 의해 냉각된 용기에서 20℃ 이하를 유지하면서 포름알데히드의 35% 수용액 H(CH2O)3OH에 에틸렌디아민 NH2(CH2)2NH 2을 서서히 적가하였다. NH2(CH2)2NH2 : CH2O의 몰비는 1: 3이다. Ethylenediamine NH 2 (CH 2 ) 2 NH 2 was slowly added dropwise to 35% aqueous solution of formaldehyde H (CH 2 O) 3 OH while maintaining the temperature below 20 ° C. in a vessel cooled by ice. The molar ratio of NH 2 (CH 2 ) 2 NH 2 : CH 2 O is 1: 3.
에틸렌디아민과 포름알데히드의 반응이 종료되면, 황화수소를 부가하여 반응시켜 흰색 분말의 디티아데카메틸렌 테트라민 S2C10H20N4을 얻었다. 수율은 91%였다. 여과하고 세척 및 건조하여 디티아데카메틸렌 테트라민 흡착제를 얻었다. 백금을 포함하는 0.05M HCl 용액 100L에 디티아데카메틸렌 테트라민 10g을 부가하였다. 40℃-50℃의 온도를 유지하면서 두시간동안 흡착시킨 다음, 흡착제를 수거하여 세척하고 건조하였다. 소각로에서 600-650℃의 온도로 소각하여 백금 5.8을 얻었다. When the reaction of ethylenediamine and formaldehyde was complete | finished, hydrogen sulfide was added and reacted to obtain white powder of dithiadecamethylene tetramine S 2 C 10 H 20 N 4 . Yield 91%. Filtration, washing and drying afforded a dithiadecamethylene tetramine adsorbent. 10 g of dithiadecamethylene tetramine was added to 100 L of 0.05 M HCl solution containing platinum. Adsorption was carried out for two hours while maintaining a temperature of 40 ° C.-50 ° C., then the adsorbent was collected, washed and dried. The incinerator was incinerated at a temperature of 600-650 ° C. to obtain platinum 5.8.
상기에서 알 수 있는 바와 같이, 본 발명의 방법에 의해 포름알데히드와 에틸렌디아민, 황화수소로부터 디티아데카메틸렌 테트라민 흡착제를 제조할 수 있다. As can be seen above, the dithiadecamethylene tetramine adsorbent can be produced from formaldehyde, ethylenediamine and hydrogen sulfide by the method of the present invention.
본 발명에 의해 제조된 디티아데카메틸렌 테트라민 흡착제는 종래의 흡착제에 비해 비교적 낮은 온도에서 분해되므로 흡착제를 소각시키기 위해 많은 에너지 소모가 필요없어 매우 경제적이다. 또한 본 발명의 흡착제는 금속 이온 중에서 귀금속에 대한 선택성이 높고 종래의 흡착제에 비해 약 20% 이상 향상된 우수한 흡착능을 나타낸다.The dithiadecamethylene tetramine adsorbent prepared by the present invention is decomposed at a relatively low temperature as compared to the conventional adsorbent, so that much energy consumption is not required to incinerate the adsorbent, which is very economical. In addition, the adsorbent of the present invention has a high selectivity for precious metals among the metal ions and shows an excellent adsorption capacity improved by about 20% or more compared to the conventional adsorbent.
또한, 본 발명의 흡착제는 산이나 알칼리 특히, 강산이나 강알칼리 등 용액의 액성에 관계없이 사용가능한 특징이 있다. In addition, the adsorbent of the present invention has a feature that can be used irrespective of the liquidity of a solution such as an acid or an alkali, particularly a strong acid or a strong alkali.
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