KR102355014B1 - Acrylic fiber with improved phosphorus adsorption capacity and producing method thereof - Google Patents
Acrylic fiber with improved phosphorus adsorption capacity and producing method thereof Download PDFInfo
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Abstract
본 발명은 인 흡착능이 개선된 아크릴계 섬유 및 이의 제조방법에 관한 것으로, 구체적으로는 아크릴계 섬유에 아민계 화합물 및 철 화합물을 반응시켜 인 흡착능이 개선된 아크릴계 섬유 및 이의 제조방법에 관한 것이다. 본 발명에 의한 아크릴계 섬유는 수질오염원인 양이온 및 음이온을 모두 흡착할 수 있으며, 특히 인의 흡착능이 우수하다. 따라서 제조공정이 간단하여 제조비용을 낮추면서도 우수한 인 흡착능이 인정되는 아크릴계 흡착 섬유 및 이를 포함하는 흡착제를 제공할 수 있으며, 상기 흡착 섬유와 흡착제는 유해가스 및 대기정화 장치, 자동차 공기정화필터, 빌딩용 공조필터, 수처리용 정화장치, 여러 희귀금속과 중금속의 분리 및 회수장치 등 각종 필터 소재로 광범위하게 활용될 수 있다.The present invention relates to an acrylic fiber having improved phosphorus adsorption capacity and a method for producing the same, and more particularly, to an acrylic fiber having improved phosphorus adsorption capacity by reacting an amine compound and an iron compound with the acrylic fiber and a method for manufacturing the same. The acrylic fiber according to the present invention can adsorb both cations and anions, which are sources of water pollution, and in particular, has excellent adsorption capacity for phosphorus. Therefore, it is possible to provide an acryl-based adsorption fiber and an adsorbent containing the same, which are recognized for their excellent phosphorus adsorption ability while lowering the manufacturing cost due to a simple manufacturing process. It can be widely used as various filter materials, such as air conditioning filters for water treatment, purification equipment for water treatment, and separation and recovery equipment for various rare and heavy metals.
Description
본 발명은 인 흡착능이 개선된 아크릴계 섬유 및 이의 제조방법에 관한 것으로, 구체적으로는 아크릴계 섬유에 아민계 화합물을 반응시킨 후, 철 화합물을 흡착시켜 인을 효과적으로 흡착할 수 있는 아크릴계 흡착 섬유 및 이의 제조방법 에 관한 것이다.The present invention relates to an acrylic fiber having improved phosphorus adsorption capacity and a method for manufacturing the same. Specifically, an acrylic fiber adsorbing fiber capable of effectively adsorbing phosphorus by adsorbing an iron compound after reacting the acrylic fiber with an amine compound and manufacturing the same it's about how
전자 및 반도체산업, 섬유산업, 식품산업, 제철 및 석유화학 등의 중화학 산업의 발달과 더불어 인구증가로 인해 발생되는 산업폐수, 생활폐수 및 가축폐수 등의 수질오염의 배출량이 증가추세에 있다. 그러나 대부분의 수질오염원들은 양이온들의 중금속과 음이온들의 인 및 질소화합물들이 함유되어 있다. 따라서 수질오염을 감소시키기 위해서는 중금속 및 인, 질소화합물의 수질오염원들을 제거해야 하며, 이들의 제거를 위해 흡착제 관련 연구가 많이 진행되고 있다.With the development of heavy and chemical industries such as electronics and semiconductor industry, textile industry, food industry, iron and petrochemical industry, the amount of water pollution such as industrial wastewater, domestic wastewater, and livestock wastewater generated due to population increase is increasing. However, most water pollutants contain heavy metals as cations and phosphorus and nitrogen compounds as anions. Therefore, in order to reduce water pollution, it is necessary to remove heavy metals, water pollution sources such as phosphorus and nitrogen compounds, and there are many studies on adsorbents for their removal.
최근, 상기와 같은 종래의 고분자수지 및 미생물을 이용하는 흡착제의 문제점을 해결하기 위해 섬유상의 흡착제들이 개발되었으며, 섬유상의 흡착제는 비드 및 분말형태보다 높은 비표면적 및 많은 기능기를 갖기 때문에 흡착능이 우수하며, 설비 운전 조건과 적용방법에 따른 모듈 설계 등 실제 응용처에 따라 다양하게 이용 가능하며 운전압력을 최소화 할 수 있는 많은 장점을 지닌다.Recently, fibrous adsorbents have been developed to solve the problems of adsorbents using conventional polymer resins and microorganisms as described above, and fibrous adsorbents have a higher specific surface area and many functional groups than beads and powders, so they have excellent adsorption capacity, It can be used in a variety of ways depending on the actual application, such as module design according to facility operating conditions and application methods, and has many advantages to minimize operating pressure.
이와 관련된 선행기술로는 한국 등록특허 제10-1521991호(수분산 폴리우레탄/히드록시아파타이트/섬유 복합 흡착재 및 이의 제조방법), 한국 등록특허 제10-1718607호(고분자 복합 섬유 제조방법 및 이의 의한 고분자 복합 섬유 흡착제) 및 한국 등록특허 제10-0952945호(휘발성 유기화합물 흡착용 섬유상 흡착제 및 이의 제조방법) 등이 있으나, 인을 흡착할 수 있는 섬유 흡착제에 대해서는 개시되어 있지 않다.As prior art related thereto, Korean Patent Registration No. 10-1521991 (water-dispersed polyurethane/hydroxyapatite/fiber composite adsorbent and manufacturing method thereof), Korean Patent No. 10-1718607 (polymer composite fiber manufacturing method and its method) polymer composite fiber adsorbent) and Korean Patent Registration No. 10-0952945 (fibrous adsorbent for adsorbing volatile organic compounds and manufacturing method thereof), but a fiber adsorbent capable of adsorbing phosphorus is not disclosed.
본 발명자들은 수질 오염의 주된 원인 중 하나인 인을 제거할 수 있는 인 흡착능이 개선된 섬유의 개발의 필요성을 느끼게 되었는바, 인 흡착능이 개선된 아크릴 섬유 및 이의 제조방법을 완성하게 되었다. The present inventors felt the need to develop a fiber with improved phosphorus adsorption capacity capable of removing phosphorus, one of the main causes of water pollution, and completed an acrylic fiber with improved phosphorus adsorption capacity and a manufacturing method thereof.
상기와 같은 목적을 달성하기 위해 본 발명은 인 흡착능이 개선된 아크릴계 섬유를 제공한다.In order to achieve the above object, the present invention provides an acrylic fiber having improved phosphorus adsorption ability.
또한, 본 발명은 상기 인 흡착능이 개선된 아크릴계 섬유의 제조방법을 제공한다.In addition, the present invention provides a method for producing an acrylic fiber having improved phosphorus adsorption ability.
본 발명의 인 흡착능이 개선된 아크릴계 섬유는 양이온 및 음이온 모두를 흡착할 수 있으나, 바람직하게는 인(phosphorus)을 특이적으로 흡착할 수 있다.The acrylic fiber having improved phosphorus adsorption capacity of the present invention can adsorb both cations and anions, but preferably can specifically adsorb phosphorus.
본 발명의 인 흡착능이 개선된 아크릴계 섬유의 합성원리는 아크릴 섬유에 있는 CN기에 아민계 화합물이 결합하여, 도 1과 같은 아크릴 흡착섬유를 합성하는 방식으로 아크릴에 아민계 화합물이 결합한 후에는 NH2기와 NH기의 배위결합 및 이온 결합으로 중금속 및 음이온을 흡착하는 원리를 이용한 것이다.In the adsorption capacity synthesis principles of the improved acrylic fibers bond is CN an amine-based compound in the acrylic fiber, after this do acrylic adsorbed to acrylic in the manner of synthesizing a fiber amine-based compounds such as 1 combination of the present invention is NH 2 It uses the principle of adsorbing heavy metals and anions through coordination and ionic bonding between the group and the NH group.
보다 구체적으로는 아크릴 섬유에 아민계 화합물을 반응시키고 이후 철 화합물을 흡착시켜 아크릴계 섬유를 합성하였고, 상기 아크릴계 섬유에 중금속을 흡착시키면 도 2와 같이 중금속이 결정 성장을 통해 흡착이 되어 인을 효과적으로 제거할 수 있다.More specifically, the acrylic fiber was reacted with an amine compound and then the iron compound was adsorbed to synthesize the acrylic fiber. When the heavy metal was adsorbed to the acrylic fiber, the heavy metal was adsorbed through crystal growth as shown in FIG. 2 and phosphorus was effectively removed. can do.
상기 아크릴계 섬유는 아크릴로니트릴, 비닐알콜, 비닐아세테이트, 비닐클로라이드, 메틸아클리레이트, 부틸아크릴레이트 및 비닐아세틱에시드, 폴리비닐아세테이트 등 일 수 있으며, 이에 제한되는 것은 아니다.The acrylic fiber may be acrylonitrile, vinyl alcohol, vinyl acetate, vinyl chloride, methyl acrylate, butyl acrylate, vinyl acetic acid, polyvinyl acetate, and the like, but is not limited thereto.
또한, 아크릴계 섬유는 상기 성분 각각 또는 조합에 의해 제조되는 것일 수 있으며, 바람직하게는 아크릴로니트릴과 폴리비닐아세테이트의 조합에 의해 제조되는 것일 수 있다.In addition, the acrylic fiber may be prepared by each or a combination of the above components, and preferably may be prepared by a combination of acrylonitrile and polyvinyl acetate.
아크릴계 섬유가 아크릴로니트릴과 폴리비닐아세테이트의 조합에 의해 제조되는 경우, 아크릴로니트릴의 함량은 아크릴계 섬유 전체 100 중량부 대비 70 내지 99 중량부로 포함될 수 있으며, 바람직하게는 80 내지 99 중량부로 포함될 수 있다. 폴리비닐아세테이트는 아크릴계 섬유 100 중량부 대비 1 내지 30 중량부로 포함될 수 있으며, 바람직하게는 1 내지 20 중량부로 포함될 수 있다. When the acrylic fiber is prepared by a combination of acrylonitrile and polyvinyl acetate, the content of acrylonitrile may be included in an amount of 70 to 99 parts by weight, preferably 80 to 99 parts by weight, based on 100 parts by weight of the total acrylic fiber. have. Polyvinyl acetate may be included in an amount of 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the acrylic fiber.
상기 아민계 화합물은 아크릴계 섬유에 반응시킬 경우 0.1 내지 30%(w/w), 바람직하게는 0.1 내지 20%(w/w) 농도로 반응시킬 수 있다. 상기 농도 보다 낮은 농도로 반응시키면 이후 철 화합물을 반응시킬 때 철 화합물이 섬유에 잘 흡착되지 않을 수 있으며, 상기 농도보다 높은 농도로 반응시키면 섬유가 손상될 수 있다.The amine-based compound may be reacted at a concentration of 0.1 to 30% (w/w), preferably 0.1 to 20% (w/w) when reacted with the acrylic fiber. If the reaction is performed at a concentration lower than the concentration, the iron compound may not be well adsorbed to the fiber when the iron compound is subsequently reacted, and if the reaction concentration is higher than the concentration, the fiber may be damaged.
상기 아민계 화합물은 에틸렌다이아민 (ethylenediamine, EDA), 다이에틸렌트라이아민(diethylenetriamine, DETA), 트리스(2-아미노에틸아민(tris(2-aminoethyl)amine), 프로판-1,3-다이아민(propane-1,3-diamine), 메테인 트라이아민(methane triamine), 3-(2-아미노에틸)프로판-1,5-다이아민(3-(2-aminoethyl)pentane-1,5-diamine), 멜라민(melamine), 디아미노푸라잔(diaminofurazan), 디아미노피리딘(diaminopyridine) 및 디아미노피리미딘(diaminopyrimidine)으로 이루어진 그룹에서 선택된 하나 이상을 포함할 수 있으며, 바람직하게는 다이에틸렌트라이아민(diethylenetriamine, DETA)일 수 있다. The amine compound is ethylenediamine (ethylenediamine, EDA), diethylenetriamine (DETA), tris (2-aminoethylamine (tris(2-aminoethyl)amine), propane-1,3-diamine ( propane-1,3-diamine), methane triamine, 3-(2-aminoethyl)propane-1,5-diamine (3-(2-aminoethyl)pentane-1,5-diamine) , melamine, diaminofurazan, diaminopyridine and diaminopyrimidine may include at least one selected from the group consisting of, preferably diethylenetriamine , DETA).
본 발명에서 인 흡착능을 개선시키기 위해 아민 화합물을 반응시킨 아크릴계 섬유에 Al, Fe, Ba, Bi, Cd, Ce, Cu, Li, Zn 등의 금속이온을 사용할 수 있으며, 이들의 구체적인 화합물로는 FePO4, AlPO4, Cu2P2O7`3H2O(피로인산구리), Ba3(PO4)2, BiPO4, Cd3(PO4)2, CePO4, Li3PO4 등이 있다. 그러나 바람직하게는 상기의 아민계 화합물을 반응시킨 아크릴계 섬유에 추가적으로 철 화합물을 반응시킬 수 있다.In the present invention, metal ions such as Al, Fe, Ba, Bi, Cd, Ce, Cu, Li, Zn, etc. can be used in the acrylic fiber reacted with an amine compound to improve phosphorus adsorption ability. 4 , AlPO 4 , Cu 2 P 2 O 7` 3H 2 O (copper pyrophosphate), Ba 3 (PO 4 ) 2 , BiPO 4 , Cd 3 (PO 4 ) 2 , CePO 4 , Li 3 PO 4 , etc. . However, preferably, an iron compound may be additionally reacted with the acrylic fiber in which the amine-based compound has been reacted.
철 화합물의 경우, 황산제일철(FeSO4), 황산제이철(Fe2(SO4)3), 염화제일철(FeCl2) 및 염화제이철 (FeCl3) 등을 사용할 수 있고 그 수화물 또한 사용이 가능하다.In the case of the iron compound, ferrous sulfate (FeSO 4 ), ferric sulfate (Fe 2 (SO 4 ) 3 ), ferrous chloride (FeCl 2 ), ferric chloride (FeCl 3 ), etc. may be used, and hydrates thereof may also be used.
상기 철 화합물은 바람직하게는 0.01 내지 0.3M의 농도로 포함되어 반응시킬 수 있다. 상기 범위를 벗어날 경우, 반응이 미반응되거나 과반응이 일어나서 섬유가 손상될 수 있다. The iron compound may be included and reacted at a concentration of preferably 0.01 to 0.3M. If it is out of the above range, the fiber may be damaged due to unreacted reaction or overreaction.
본 발명은 상기 아크릴계 섬유에 아민 화합물 및 철 화합물을 반응시켜 인 흡착능을 개선시킬 수 있으며, 아민 화합물 또는 철 화합물 반응시 필요한 경우 촉매를 사용할 수 있다.In the present invention, phosphorus adsorption capacity can be improved by reacting the acrylic fiber with an amine compound and an iron compound, and a catalyst can be used if necessary in the reaction of the amine compound or iron compound.
상기 촉매는 염화알루미늄 수화물, 염화알루미늄, 탄산나트륨(Na2CO3) 등에서 선택할 수 있으며, 바람직하게는 염화알루미늄 6 수화물(AlCl2·6H2O)을 사용할 수 있다. The catalyst may be selected from aluminum chloride hydrate, aluminum chloride, sodium carbonate (Na 2 CO 3 ), and the like, and preferably aluminum chloride hexahydrate (AlCl 2 .6H 2 O).
또한, 상기 촉매는 아크릴계 섬유 100 중량 대비 0.1~30 중량부 투입될 수 있으며, 바람직하게는 10~15 중량부 투입될 수 있다. 상기 범위 미만으로 투입될 경우, 아크릴계 섬유와 아민 화합물의 반응이 진행되지 않을 수 있으며, 상기 범위를 초과하여 투입될 경우 아민간의 결합을 빠르게 일으켜 아크릴계 섬유의 표면 개질에 적합하지 않다.In addition, the catalyst may be added in an amount of 0.1 to 30 parts by weight, preferably 10 to 15 parts by weight, based on 100 parts by weight of the acrylic fiber. When the amount is less than the above range, the reaction between the acrylic fiber and the amine compound may not proceed, and when the amount exceeds the above range, the bonding between the amines occurs quickly, which is not suitable for surface modification of the acrylic fiber.
아민계 화합물 또는 철 화합물에 촉매를 넣어 반응시킬 때에는 50 내지 150℃의 온도 범위에서 진행될 수 있으며, 바람직하게는 90 내지 120℃에서 진행될 수 있다. 상기 반응의 반응 온도가 50℃ 미만이면 상기 아크릴계 섬유와 아민 화합물의 반응이 원활하지 않을 수 있으며, 상기 반응 온도가 150℃를 초과하는 경우 상기 아크릴계 섬유가 아민 용액에 녹아 최종 생성되는 흡착 섬유의 인 흡착능이 저하될 수 있다.When the catalyst is added to the amine-based compound or the iron compound, the reaction may be carried out at a temperature range of 50 to 150°C, preferably at 90 to 120°C. If the reaction temperature of the reaction is less than 50 ℃, the reaction between the acrylic fiber and the amine compound may not be smooth. Adsorption capacity may be reduced.
상기 아크릴계 섬유와 아민 화합물, 철 화합물의 반응은 30분 내지 120 분 범위 내의 시간 동안 진행될 수 있다. 상기 반응이 30분 미만으로 진행되는 경우 반응의 수율이 낮아 상기 아크릴계 흡착 섬유의 수득률이 낮게 형성되고, 상기 반응이 120분을 초과하여 진행되는 경우 최종 생성되는 흡착 섬유가 섬유의 특징을 갖지 못할 수 있다.The reaction of the acrylic fiber with the amine compound and the iron compound may be carried out for a time in the range of 30 minutes to 120 minutes. If the reaction proceeds for less than 30 minutes, the yield of the reaction is low and the yield of the acrylic adsorption fiber is low, and if the reaction proceeds for more than 120 minutes, the final adsorption fiber may not have the characteristics of the fiber have.
본 발명에 따른 인 흡착능이 개선된 아크릴계 흡착 섬유는 5 내지 30 mmol/g 범위의 인 흡착능을 보일 수 있고, 바람직하게는 9 내지 30 mmol/g 범위의 인 흡착능을 보일 수 있다. The acrylic adsorption fiber having improved phosphorus adsorption capacity according to the present invention may exhibit a phosphorus adsorption capacity in the range of 5 to 30 mmol/g, and preferably may exhibit a phosphorus adsorption capacity in the range of 9 to 30 mmol/g.
또한, 흡착섬유의 색은 노란색으로 직경은 5 내지 60㎛일 수 있으며, 바람직하게는 10~50㎛일 수 있다. In addition, the color of the adsorbent fibers may be yellow and may have a diameter of 5 to 60 μm, preferably 10 to 50 μm.
상기 흡착섬유는 =NH, -NH2 기능기를 포함할 수 있다.The adsorption fiber may include =NH, -NH 2 functional groups.
또한, 본 발명은 (a) 아크릴계 섬유에 아민 화합물을 반응시키는 단계;In addition, the present invention comprises the steps of (a) reacting an amine compound to the acrylic fiber;
(b) 상기 (a) 단계에서 반응시킨 아크릴계 섬유에 철 화합물을 반응시키는 단계;(b) reacting an iron compound with the acrylic fiber reacted in step (a);
를 포함하는 인 흡착능이 개선된 아크릴계 섬유의 제조방법을 제공한다.It provides a method for producing an acrylic fiber having improved phosphorus adsorption capacity, comprising:
상기 (a), (b) 단계에서 필요한 경우, 촉매를 추가하는 단계를 추가로 포함할 수 있다.If necessary in the steps (a) and (b), the step of adding a catalyst may be further included.
본 발명은 수질오염원인 양이온 및 음이온을 모두 흡착할 수 있으며, 특히 인의 흡착력이 우수하다. 따라서 제조공정이 간단하여 제조비용을 낮추면서도 우수한 인 흡착능이 인정되는 아크릴계 흡착 섬유 및 이를 포함하는 흡착제를 제공할 수 있다. The present invention can adsorb both cations and anions, which are sources of water pollution, and in particular, has excellent adsorption power of phosphorus. Therefore, it is possible to provide an acryl-based adsorption fiber having excellent phosphorus adsorption ability while lowering manufacturing cost due to a simple manufacturing process and an adsorbent including the same.
상기 흡착 섬유와 흡착제는 유해가스 및 대기정화 장치, 자동차 공기정화필터, 빌딩용 공조필터, 수처리용 정화장치, 여러 희귀금속과 중금속의 분리 및 회수장치 등 각종 필터 소재로 광범위하게 활용될 수 있다.The adsorbent fibers and adsorbents can be widely used as various filter materials, such as harmful gas and air purification devices, automobile air purification filters, air conditioning filters for buildings, purification devices for water treatment, and separation and recovery devices for various rare and heavy metals.
도 1은 본 발명의 아크릴계 섬유의 합성 원리를 도시한 것이다.
도 2는 본 발명의 아크릴계 섬유의 합성 원리 및 중금속 등의 흡착원리를 나타낸 것이다.
도 3은 본 발명의 실시예1 및 비교예 1의 아크릴계 섬유의 인 흡착 실험 결과를 나타낸 것이다.
도 4는 본 발명의 아크릴계 섬유의 합성시 아민 및 철의 농도를 달리하였을 때의 인 흡착량 결과를 나타낸 것이다.
도 5는 시간, pH에 따른 본 발명의 아크릴계 섬유의 인 흡착률 결과를 나타낸 것이다.1 shows the synthesis principle of the acrylic fiber of the present invention.
2 shows the principle of synthesizing the acrylic fiber of the present invention and the principle of adsorption of heavy metals and the like.
3 shows the phosphorus adsorption test results of the acrylic fibers of Example 1 and Comparative Example 1 of the present invention.
4 shows the results of the phosphorus adsorption amount when the concentrations of amine and iron are different during the synthesis of the acrylic fiber of the present invention.
5 shows the phosphorus adsorption rate results of the acrylic fiber of the present invention according to time and pH.
이하, 본 발명을 실시예 및 실험예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of Examples and Experimental Examples.
단, 하기 실시예 및 실험예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예 및 실험예에 한정되는 것은 아니다.However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.
<실시예 1><Example 1>
본 발명의 인 흡착 섬유를 하기와 같은 방법에 의해 제조하였다;The phosphorus adsorption fiber of the present invention was prepared by the following method;
반응은 3구 플라스크에서 진행하였다. 아크릴계 섬유로서 사용되는 아크릴로나이트릴 90%, 폴리비닐아세테이트 10%의 공중합체 섬유 5g과 DETA 200ml, 촉매 염화알루미늄 6수화물(AlCl2·6H2O)은 섬유의 전체 중량 대비 10중량%(0.5g) 첨가하였다. 반응 전, 용매인 DETA가 섬유에 잘 스며들게 하여 100℃에서 1시간 동안 반응시켰다. 반응이 끝난 후, 찬물로 여러번 씻어 용매와 촉매를 씻어낸 뒤 50℃ 진공오븐에서 1시간 동안 건조하였다. 건조한 섬유 일부는 0.1M FeCl3 수용액에 넣어 교반시켜 반응하였고, 반응 후에는 물로 세척시켜 건조하였다.The reaction was carried out in a three-necked flask. 5 g of copolymer fibers of 90% acrylonitrile, 10% polyvinyl acetate, and 200 ml of DETA, catalyst aluminum chloride hexahydrate (AlCl 2 .6H 2 O) used as acrylic fibers are 10% by weight (0.5%) of the total weight of the fiber. g) added. Before the reaction, DETA, a solvent, was allowed to permeate the fibers and reacted at 100° C. for 1 hour. After the reaction was completed, the mixture was washed several times with cold water to wash the solvent and catalyst, and then dried in a vacuum oven at 50° C. for 1 hour. A part of the dried fibers were put in 0.1M FeCl 3 aqueous solution and stirred to react, and after the reaction, washed with water and dried.
<실시예 2 내지 5><Examples 2 to 5>
아민 개질반응은 1kg 염색 반응기에서 진행하였다. 아크릴계 섬유로서 사용되는 아크릴로나이트릴 90%, 폴리비닐아세테이트 10%의 공중합체 섬유를 다공성케이스에 넣어 반응기에 장착 후 고정하였다. 다이에틸렌트라이아민(Diethylenetriamine, DETA)을 물에 섞어 각각 5, 10, 15, 20%(w/w) 농도로 하고, 촉매로 AlCl2·6H2O을 사용하여 반응기에 주입하였다. 이 때, 아크릴계 섬유 대 DETA 비율을 1 : 20 중량비로 하고, 촉매는 사용된 섬유의 100 중량부 대비 10 중량부를 DETA 수용액에 넣어 90℃에서 2시간 동안 반응시켰다. 반응 후 섬유를 찬 물로 여러 번 세척하여 용매와 촉매를 씻어내고 탈수, 건조시켰다.The amine reforming reaction was carried out in a 1 kg dyeing reactor. Copolymer fibers of 90% acrylonitrile and 10% polyvinyl acetate used as acrylic fibers were placed in a porous case, mounted in a reactor, and fixed. Diethylenetriamine (DETA) was mixed with water to a concentration of 5, 10, 15, and 20% (w/w), respectively, and AlCl 2 ·6H 2 O was used as a catalyst and injected into the reactor. At this time, the ratio of acrylic fiber to DETA was 1:20 by weight, and the catalyst was put into an aqueous DETA solution in 10 parts by weight based on 100 parts by weight of the fiber used and reacted at 90° C. for 2 hours. After the reaction, the fibers were washed several times with cold water to wash off the solvent and catalyst, and then dehydrated and dried.
상기에서 합성된 흡착 섬유 1kg를 준비하여 반응기 케이스에 넣었고, 철 화합물로 0.1M FeCl3 30L를 제조하여 염색반응기에 넣어 반응기 케이스와 반응기를 조립하고 염색반응기 뚜껑을 닫았다. 30℃에서 1시간 동안 반응시켜, 이온교환 섬유에 철을 흡착시켰다. 아민 농도를 5, 10, 15, 20%(w/w)로 각각 달리하여 제조한 섬유에 철을 흡착시켰으며, 반응 후 철 수용액을 버리고 물로 충분히 세척하여 제조한 섬유를 탈수 후, 건조시켰다.1 kg of the adsorbed fiber synthesized above was prepared and put in a reactor case, 0.1M FeCl 3 30L of iron compound was prepared and put into the dyeing reactor, the reactor case and the reactor were assembled, and the dyeing reactor lid was closed. By reacting at 30° C. for 1 hour, iron was adsorbed to the ion exchange fiber. Iron was adsorbed to the fibers prepared by varying the amine concentration at 5, 10, 15, and 20% (w/w), respectively, and after the reaction, the iron aqueous solution was discarded and washed sufficiently with water to dehydrate the prepared fibers and then dried.
<실시예 6><Example 6>
실시예 5와 같은 방법으로 수행하되, 철 화합물은 FeCl3가 아닌 FeCl2를 사용하였다.It was carried out in the same manner as in Example 5, but FeCl 2 was used instead of FeCl 3 as the iron compound.
<실시예 7><Example 7>
실시예 5와 같은 방법으로 수행하되, 철 화합물은 FeCl3가 아닌 황산제일철(FeSO4)를 사용하였다.It was carried out in the same manner as in Example 5, except that the iron compound was not FeCl 3 , but ferrous sulfate (FeSO 4 ) was used.
<실시예 8><Example 8>
실시예 5와 같은 방법으로 수행하되, 철 화합물은 FeCl3가 아닌 황산제이철(Fe2(SO4)3)를 사용하였다.It was carried out in the same manner as in Example 5, except that the iron compound was not FeCl 3 , but ferric sulfate (Fe 2 (SO 4 ) 3 ) was used.
<비교예 1><Comparative Example 1>
상기 실시예 1의 제조과정에서 철 화합물을 흡착 시킨 것을 제외하고 동일하게 제조하였다.It was prepared in the same manner except that the iron compound was adsorbed in the manufacturing process of Example 1.
<비교예 2 내지 5><Comparative Examples 2 to 5>
상기 실시예 2 내지 5의 제조과정에서 철 화합물을 흡착 시킨 것을 제외하고 동일하게 제조하였고, 아민의 농도는 5, 10, 15, 20%(w/w)로 달리하여 제조하였다. It was prepared in the same manner except that the iron compound was adsorbed in the preparation process of Examples 2 to 5, and the concentration of the amine was varied by 5, 10, 15, and 20% (w/w).
<비교예 6><Comparative Example 6>
실시예 6의 제조과정에서 철 화합물을 흡착 시킨 것을 제외하고, 동일하게 제조하였다.Except that the iron compound was adsorbed in the manufacturing process of Example 6, it was prepared in the same manner.
<실험예> 인 흡착 성능 평가 <Experimental Example> Evaluation of phosphorus adsorption performance
1. 흡착섬유 실험1. Adsorption fiber experiment
비교예 1 및 실시예1 제조된 아민처리만 한 섬유와 철 화합물까지 처리한 본 발명의 아크릴계 섬유를 ICP-OES를 이용하여 인 흡착능을 분석하였다. 흡착실험은 본 발명의 아크릴계 섬유 0.1g을 100ml의 제조된 인 수용액에 넣어 진행하였다. 상기 제조된 용액은 100mM로 제조되었고, 흡착실험 시간은 24시간 진행하여 최대 흡착능을 도출하도록 실험 진행하였다. Comparative Example 1 and Example 1 Phosphorus adsorption capacity was analyzed for the prepared amine-treated fibers and the acrylic fibers of the present invention treated with iron compounds using ICP-OES. The adsorption experiment was carried out by putting 0.1 g of the acrylic fiber of the present invention in 100 ml of the prepared phosphorus aqueous solution. The prepared solution was prepared at 100 mM, and the adsorption experiment time was carried out for 24 hours to derive the maximum adsorption capacity.
그 결과, 아민처리만 한 비교예 1은 5mmol/g의 성능을 보이나 철 화합물 처리한 실시예 1는 9mmol/g이상의 인 흡착능력을 확인할 수 있었다(도 3).As a result, Comparative Example 1 treated with only amine showed a performance of 5 mmol/g, but Example 1 treated with an iron compound showed a phosphorus adsorption capacity of 9 mmol/g or more (FIG. 3).
2. 아민 농도별 인 흡착능 실험2. Phosphorus adsorption capacity test by amine concentration
비교예 2 내지 6 및 실시예 2 내지 5에 따라 제조한 섬유의 인 흡착능을 분석하였다. 흡착실험은 본 발명의 아크릴계 섬유 0.1g을 100ml의 제조된 인 수용액에 넣어 진행하였다. 상기 제조된 용액은 100mM로 제조되었고, 흡착실험 시간은 24시간 진행하여 최대 흡착능을 도출하도록 실험을 진행하였다.The phosphorus adsorption capacity of the fibers prepared according to Comparative Examples 2 to 6 and Examples 2 to 5 was analyzed. The adsorption experiment was carried out by putting 0.1 g of the acrylic fiber of the present invention in 100 ml of the prepared phosphorus aqueous solution. The prepared solution was prepared at 100 mM, and the adsorption experiment time was carried out for 24 hours to derive the maximum adsorption capacity.
실험결과, 비교예 2 내지 6보다 실시예 2 내지 5의 흡착능이 높았고, 실시예 1에 제조한 아크릴계 섬유와 흡착율 크게 차이가 나지 않았음을 확인하였다(도 4).As a result of the experiment, it was confirmed that the adsorption capacity of Examples 2 to 5 was higher than that of Comparative Examples 2 to 6, and the adsorption rate was not significantly different from that of the acrylic fiber prepared in Example 1 ( FIG. 4 ).
3. 시간 및 pH에 따른 인 흡착력 평가3. Evaluation of phosphorus adsorption capacity according to time and pH
본 발명의 실시예 5의 흡착섬유의 인 흡착력을 시간 및 pH를 달리하여 평가하였고 그 결과는 도 5에 도시하였다.The phosphorus adsorption capacity of the adsorption fibers of Example 5 of the present invention was evaluated by varying the time and pH, and the results are shown in FIG. 5 .
실험결과, 아민처리만 한 비교예7 은 pH2에서 24시간 동안 반응시켰을 때 인 흡착력이 가장 우수하였다. 다만, pH3.8에서는 시간에 관계없이 흡착능이 비슷하게 나타났다. 이와 달리 철 화합물을 처리한 아크릴계 섬유인 실시예 5는 pH2에서는 아민만 처리한 것보다 약 2배 이상 인 흡착력이 증가하였고, pH3.8에서는 3시간 반응시 30%이상, 24시간 반응시에는 약 2배 이상 흡착력이 증가하였다(도 5).As a result of the experiment, Comparative Example 7 treated with only amine had the best phosphorus adsorption ability when reacted at
Claims (11)
(b) 상기 (a) 단계에서 반응시킨 아크릴계 섬유를 철 화합물은 0.01 내지 0.3M 농도로 반응시키는 단계;
를 포함하는, 인 흡착능이 5 내지 30 mmol/g 범위로 개선된 아크릴계 섬유의 제조방법.(a) acrylonitrile is included in 90 parts by weight based on 100 parts by weight of the total acrylic fiber, and polyvinyl acetate is diethylenetriamine (DETA) 10 as an amine compound to the acrylic fiber included in 10 parts by weight based on 100 parts by weight of the acrylic fiber to 20% (w/w) concentration, and the acrylic fiber to DETA ratio is 1:20 by weight;
(b) reacting the acrylic fiber reacted in step (a) with an iron compound at a concentration of 0.01 to 0.3M;
A method for producing an acrylic fiber having an improved phosphorus adsorption capacity in the range of 5 to 30 mmol/g, comprising:
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