KR20070014260A - The precipitation of heavy metal adsorbant derived from natural materials and the product thereof - Google Patents

The precipitation of heavy metal adsorbant derived from natural materials and the product thereof Download PDF

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KR20070014260A
KR20070014260A KR1020050068708A KR20050068708A KR20070014260A KR 20070014260 A KR20070014260 A KR 20070014260A KR 1020050068708 A KR1020050068708 A KR 1020050068708A KR 20050068708 A KR20050068708 A KR 20050068708A KR 20070014260 A KR20070014260 A KR 20070014260A
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South Korea
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chitosan
heavy metal
adsorbent
phosphoric acid
solution
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KR1020050068708A
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Korean (ko)
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서강수
정영진
정용식
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주식회사 다산솔루션
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Priority to KR1020050068708A priority Critical patent/KR20070014260A/en
Publication of KR20070014260A publication Critical patent/KR20070014260A/en

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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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0259—Compounds of N, P, As, Sb, Bi
    • 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
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

An adsorbent which is excellent in heavy metal adsorption capacity, is capable of being used in various environments irrespective of pH, is inexpensive, and does not cause environmental pollution even when the adsorbent is disused, and a preparation method of the same are provided. A preparation method of a heavy metal adsorbent derived from natural materials comprises: a process(a) of dissolving chitosan into an acetic acid solution and mixing the chitosan dissolved solution with a phosphoric acid solution to prepare a chitosan/phosphoric acid mixed solution; a process(b) of titrating the obtained chitosan/phosphoric acid mixed solution into a calcium hydroxide suspension to synthesize hydroxyapatite; a process(c) of washing the obtained chitosan/hydroxyapatite composite with distilled water, press-dewatering the washed chitosan/hydroxyapatite composite, molding the press dewatered chitosan/hydroxyapatite composite in a mold, and drying a resulting molded material.

Description

천연물질 유래 중금속 흡착제의 제조방법 및 그 제조물{The precipitation of heavy metal adsorbant derived from natural materials and the product thereof}The precipitation of heavy metal adsorbant derived from natural materials and the product approximately}

본 발명은 키토산/수산화아파타이트로 이루어진 천연물질 유래 중금속 흡착제의 제조방법에 관한 것으로서, 음료수 티백에 함유하도록 사용하는 경우 음료수속에 포함되어 있을 수 있는 중금속 및 유무기물을 흡착할 수 있는 흡착제에 관한 것이다.The present invention relates to a method for preparing a heavy metal adsorbent derived from a natural substance consisting of chitosan / hydroxyapatite, and when used to be contained in a beverage tea bag, the present invention relates to an adsorbent capable of adsorbing heavy metals and organic matters that may be included in a beverage.

현재 우리는 수돗물이나 생수를 음용수로 많이 사용하고 있다. 그러나 상기 수돗물이나 생수는 하천이나 저수지 또는 지하수를 수원지로 하고 있으며 음용수로 사용하기 위해서 대장균이나 기타 오염물질을 어느 정도까지는 제거하고 있다. Currently, we use tap water or bottled water as drinking water. However, the tap water and the bottled water are rivers, reservoirs, or groundwater as the source of water, and E. coli or other contaminants are removed to some extent for use as drinking water.

그러나 니켈, 카드뮴, 수은 등의 중금속이 하천이나 지하수층에 유출되면 그로부터 제조된 수돗물이나 생수에도 중금속이 잔류하게 되어 이를 사람이 마시게 되어 카드뮴과 수은이 인체에 축적될 경우 각각 이따이이따이병과 미나마타병을 일으키고 납은 중추신경계와 심장, 간기능에 손상을 주는 등 치명적인 문제가 발생된다. 특히 광산주변의 경우 지하수에서 인체에 치명적인 중금속인 납과 비소가 먹는 물 수질기준을 초과하여 검출되는 경우가 많고, 먹는물에 있어서는 안 되는 수은이 검출될 수 있는 위험도 가지고 있다.However, when heavy metals such as nickel, cadmium, and mercury spill into rivers or groundwater layers, heavy metals remain in tap water or bottled water produced therefrom, and they are consumed by humans. When cadmium and mercury accumulate in the human body, Lead causes fatal problems, including damage to the central nervous system, heart, and liver function. Particularly, in the vicinity of mines, lead and arsenic, which are fatal metals, which are fatal to humans, are often detected in excess of the drinking water quality standards, and there is a danger of detecting mercury which should not be in drinking water.

이러한 중금속을 제거하기 위해서는 킬레이트기를 가지는 수지로써 중금속을 선택적으로 이온교환하도록 하여 제거할 수 있으나 이러한 수지는 가격이 비싸고 유효 pH범위가 한정되어 그 응용범위가 넓지 못하며, 폐기시 환경오염의 문제점이 있다.To remove such heavy metals, it is possible to remove them by selectively ion-exchanging heavy metals as a resin having a chelating group, but these resins are expensive and the effective pH range is limited, so the application range is not wide, and there is a problem of environmental pollution when disposed. .

따라서 본 발명은 상기 종래기술의 문제점을 극복하여 중금속흡착능력이 우수하며 pH에 구애받지 않아 다양한 환경에서 사용할 수 있을 뿐만 아니라 저렴하면서도 폐기하는 경우에도 환경오염을 일으키지 않는 흡착제를 제공하는 것을 기술적 과제로 한다.Therefore, the present invention is to overcome the problems of the prior art is excellent in heavy metal adsorption capacity and can be used in a variety of environments do not depend on pH, as well as to provide an adsorbent that is inexpensive and does not cause environmental pollution even when discarded as a technical problem do.

상기 기술적 과제를 해결하기 위해 본 발명자는 키토산/수산화아파타이트 복합체가 중금속 흡착능이 우수하고 환경오염도 일으키지 않을 수 있다는 것을 알고 본 발명을 완성한 것이다.In order to solve the above technical problem, the present inventors have completed the present invention knowing that the chitosan / hydroxyapatite composite may have excellent heavy metal adsorption capacity and may not cause environmental pollution.

그러므로 본 발명에 의하면 a)초산 용액으로 키토산을 용해시킨 후 인산 용액과 혼합하여 키토산/인산 혼합액을 제조하는 공정, b)얻어진 키토산/인산 혼합액을 수산화칼슘 현탁액에 적하시켜 수산화아파타이트를 합성하는 공정, c)얻어진 키 토산/수산화아파타이트 복합체를 증류수로 수세한 후 압착탈수하고 몰드에서 성형한 후 건조시키는 공정으로 이루어지는 것을 특징으로 하는 천연물질 유래 중금속 흡착제의 제조방법이 제공된다.Therefore, according to the present invention, a) dissolving chitosan in acetic acid solution and mixing with phosphoric acid solution to produce chitosan / phosphate mixture, b) dropping the obtained chitosan / phosphate mixture into calcium hydroxide suspension to synthesize apatite, c There is provided a method for producing a natural metal-derived heavy metal adsorbent, comprising a step of washing the obtained chitosan / hydroxyapatite composite with distilled water, compressing and dehydrating, molding in a mold, and drying.

이하 본 발명을 보다 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail.

본 방법은 공침전법으로 제조된 수산화아파타이트 나노입자를 함유하는 키토산 복합체를 저온건조에 의한 고밀도 비드로 만들어 흡착제를 제조하는 방법에 관한 것이다.The present method relates to a method for preparing an adsorbent by making chitosan composites containing apatite hydroxide nanoparticles prepared by coprecipitation into high-density beads by low temperature drying.

본 발명의 원료 중 하나인 키토산은 주로 해양에서 서식하는 갑각류의 껍질로부터 얻은 키틴을 탈아세틸화하여 얻을 수 있고, 그 생산량도 연간 1000억 톤 정도의 무한한 생물자원으로 인체에 무해한 천연고분자로 항균성, 항곰팡이성, 생분해성, 생체친화성, 응집작용, 중금속 흡착작용 등 많은 기능을 갖고 있으며, 키토산은 글루코사민 피라노스(glucosamine pyranose)환 1개당 1개의 아미노기와 2개의 히드록시기가 존재하고 있어 주로 중금속 흡착제로 사용되어지고 있다.Chitosan, one of the raw materials of the present invention, can be obtained by deacetylating chitin obtained from the shells of shellfish inhabiting the ocean mainly, and its production amount is 100 billion tons per year of infinite biological resources. It has many functions such as antifungal, biodegradable, biocompatible, cohesive and heavy metal adsorption, and chitosan mainly contains one amino group and two hydroxy groups per glucosamine pyranose ring. It is used as.

본 발명에서는 초산 용액으로 키토산을 용해시켜 키토산 용액을 제조하고 상기의 키토산 용액을 인산 용액과 혼합하는데 이렇게 얻어진 키토산/인산 혼합액을 수산화칼슘(Ca(OH)2 )현탁액에 적하시키게 되면 인산과 수산화칼슘이 반응하여 수산화아파타이트가 합성된다.   In the present invention, a chitosan solution is prepared by dissolving chitosan in acetic acid solution, and the chitosan solution is mixed with a phosphoric acid solution. When the chitosan / phosphate mixture thus obtained is added dropwise to a calcium hydroxide (Ca (OH) 2) suspension, phosphoric acid and calcium hydroxide react. Thus, apatite hydroxide is synthesized.

상기 수산화아파타이트는 칼슘 포스페이트계 세라믹으로, 인체의 뼈를 구성하는 주성분으로 골 전도성, 생체 활성, 생체 친화성, 이온교환반응에 의한 중금속 흡착능력이 우수하고, 단백질 흡착능력이 우수하여 정형외과나 치의학 분야의 골 대체제 뿐만 아니라 정수기용 필터소재로 사용되어 오고 있으나, 너무 딱딱하고 부서지기 쉬워 특정한 모양으로 성형가공이 어려운 문제점을 갖고 있다. 따라서 본 발명에서는 키토산과 복합하여 단점을 보완할 수 있다.The apatite hydroxide is a calcium phosphate-based ceramic, the main component constituting the bone of the human body has excellent bone conductivity, bioactivity, biocompatibility, adsorption of heavy metals by ion exchange reaction, and excellent protein adsorption ability, so that orthopedic or dental It has been used as a filter material for water purifiers as well as bone substitutes in the field, but it is too hard and brittle, and has a problem in that a molding process is difficult in a specific shape. Therefore, in the present invention, it is possible to compensate for the disadvantage by combining with chitosan.

본 발명에서는 상기와 같이 제조한 수산화아파타이트/ 키토산 복합체에 폴리카르복시산을 수산화아파타이트 중량에 대해서 첨가하는데 이때 사용되는 폴리카르복시산으로는 구연산, 부탄테트라카르복시산, 사과산 등을 사용할 수 있다. 첨가된 폴리카르복시산은 수산화아파타이트/키토산 복합체상에서 이온화되고 카르복시기는 키토산의 이온화된 아미노기와 이온결합을 형성할 수 있고, 동시에 수산화아파타이트 표면의 칼슘 이온에 대해서 포스페이트 이온보다 친화력이 높은 카르복시산 이온의 이온교환이 발생하고, 모노덴테이트(monodentate)방식이나 바이덴테이트(bidentate)방식 중 적어도 어느 한 방식으로 결합함으로서 키토산 용액상의 수산화아파타이트 나노입자들의 결정성장을 방지함으로써 수산화아파타이트 나노입자의 고른 분산상태를 유지시킬 수 있다.   In the present invention, the polycarboxylic acid is added to the apatite hydroxide / chitosan composite prepared as described above with respect to the weight of the apatite hydroxide. Citric acid, butanetetracarboxylic acid, malic acid, and the like may be used as the polycarboxylic acid. The added polycarboxylic acid is ionized on the hydroxide apatite / chitosan complex and the carboxyl group can form an ionic bond with the ionized amino group of chitosan, while at the same time ion exchange of carboxylic acid ions having a higher affinity than phosphate ions for calcium ions on the surface of the apatite hydroxide It can be generated and combined with at least one of monodentate or bidentate methods to prevent the crystal growth of the apatite hydroxide nanoparticles in chitosan solution, thereby maintaining the even dispersion state of the apatite hydroxide nanoparticles. Can be.

상기 제조한 수산화아파타이트/키토산 복합체를 물에 충분히 수세하여, 필터프레스나 원심분리기로 탈수하여 여분의 물을 제거하고 직경 5㎜ 길이 5㎜의 원통형으로 성형한 후 그늘에서 서서히 건조하면 단단한 고밀도의 원통형 수산화아파타이트/키토산 복합체 비드가 얻어진다. 키토산 산성염 수용액은 알칼리 용액에서 중화되면 팽윤도가 1,000% 정도의 겔상태를 이루고 이러한 고팽윤성 상태의 키토산 겔이 상온에서 서서히 건조되면 고수축이 일어나 밀도가 치밀한 구조를 얻을 수 있 다. The apatite hydroxide / chitosan composite prepared above was washed with water sufficiently, dewatered by a filter press or a centrifuge to remove excess water, and then formed into a cylindrical shape having a diameter of 5 mm and a length of 5 mm, and then dried slowly in the shade. Apatite hydroxide / chitosan composite beads are obtained. When the chitosan acid salt solution is neutralized in an alkaline solution, a swelling degree of gel state is about 1,000%, and when the chitosan gel in this high swellable state is slowly dried at room temperature, high shrinkage occurs to obtain a dense structure.

상기 고밀도의 원통형 수산화아파타이트/키토산 복합체 비드는 이온교환반응에 의한 중금속 흡착능력이 우수하고, 단백질 흡착능력이 우수한 데, 비드를 음료용이나 한약용 티백 주머니에 넣고 음료를 우려내거나 한약을 다리면 음료나 한약 추출액에 있을 수 있는 중금속을 비드가 흡착 제거하게 된다.The high-density cylindrical hydroxide apatite / chitosan composite beads are excellent in adsorption of heavy metals by ion exchange reaction, and have excellent protein adsorption capacity. The beads are placed in a beverage or herbal tea bag pouch and soaked in beverages, or Chinese medicine drinks. The beads will adsorb and remove heavy metals that may be present in the herbal extracts.

이렇게 사용한 비드는 재사용이 불가능하지만 키토산과 칼슘포스페이트계 세라믹으로 구성되어 있으므로 폐기하여도 환경오염의 문제가 없으며 비료 등으로 사용하여도 좋다.The beads used in this way are not reusable but are composed of chitosan and calcium phosphate-based ceramics, so there is no problem of environmental pollution even when discarded.

본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 본 발명의 보호범위를 한정하거나 제한하고자 하는 것은 아니다.The present invention may be better understood by the following examples, which are intended for the purpose of illustrating the invention and are not intended to limit or limit the scope of the invention.

[실시예 1]Example 1

2.5kg의 키토산, 1.5kg의 초산, 5.9kg의 인산을 200℃의 물에 용해시켜 혼합액을 제조한 후 7.4kg의 수산화칼슘 현탁액에 상기 혼합액을 적하시키고, 이 때 고속으로 pH 9 ± 0.2가 될 때까지 반응 온도는 25℃에서 상기 현탁액을 24시간 동안 지속적으로 교반하여 중량비 80:20의 수산화아파타이트 나노입자를 함유하는 키토산 복합체를 제조하였다. 제조된 복합체를 증류수로 수세한 후 필터프레스를 사용하여 압착 탈수하여 여분의 물을 제거하고, 고점도 슬러리 상태의 복합체를 직경 5㎜ 길이 5㎜의 원통형 틀에 넣어서 성형한 후 상온에서 서서히 건조시켜 비드를 제 조하였다.2.5 kg of chitosan, 1.5 kg of acetic acid, and 5.9 kg of phosphoric acid were dissolved in water at 200 ° C. to prepare a mixture, and the mixture was added dropwise to 7.4 kg of calcium hydroxide suspension at a high pH of 9 ± 0.2. Until the reaction temperature was continuously stirred for 24 hours at 25 ℃ to prepare a chitosan complex containing apatite hydroxide nanoparticles in a weight ratio of 80:20. The prepared composite was washed with distilled water, and then compressed and dehydrated using a filter press to remove excess water. The composite having a high viscosity slurry was placed in a cylindrical mold having a diameter of 5 mm and a length of 5 mm, and then slowly dried at room temperature. Was prepared.

건조된 복합체 비드 1g을 티백에 넣고 중금속 용액 Pb(납), Cd(카드뮴), Hg(수은)이 100ppm 함유되어 있는 100㎖의 용액을 넣고, 95℃에서 3시간 동안 밀폐된 용기에서 가열 교반하였다. 이후 ICP를 이용하여 각각의 중금속 용액내의 중금속 함량을 측정하여 제거율을 계산하여 표 1에 나타내었다.1 g of the dried composite beads were placed in a tea bag, and 100 ml of a solution containing 100 ppm of heavy metal solutions Pb (lead), Cd (cadmium), and Hg (mercury) was added thereto, and the mixture was heated and stirred in a sealed container at 95 ° C. for 3 hours. . Since ICP was used to determine the removal rate by measuring the heavy metal content in each heavy metal solution is shown in Table 1.

[비교예 1]Comparative Example 1

4%의 키토산 수용액을 5 %의 NaOH 용액에 한방울씩 적하하여 키토산만으로 이루어진 비드를 제조하였다. 제조된 비드를 충분히 수세한 후 상온에서 건조하여 실시예 1의 방법으로 중금속 제거 테스트를 실시하여 표 1에 나타내었다.4% aqueous chitosan solution was added dropwise to 5% NaOH solution to prepare beads consisting of chitosan only. After washing the prepared beads sufficiently and dried at room temperature to perform a heavy metal removal test by the method of Example 1 shown in Table 1.

Pb (%)Pb (%) Cd (%)Cd (%) Hg (%)Hg (%) 실시예 1Example 1 91.291.2 92.892.8 86.886.8 비교예 1Comparative Example 1 4646 2323 2626

본 발명에 의해 청량음료, 녹즙, 음료수, 한약 등에 포함되어 있을지 모르는 중금속을 본 발명의 흡착제 비드가 담겨진 티백을 이용하여 쉽고 효과적으로 제거할 수 있으며, 특히 한약재에서 규제하는 4대 중금속(납, 카드뮴, 수은, 비소)에 대해서도 우수한 제거 성능을 보이고 있다. 본 발명의 흡착제는 사람에게 유익한 성분들로 이루어져있을 뿐 아니라 고도의 항균성능까지 보유하고 있어 한약재 외에도 안전성이 중요시되는 식품분야에서 앞으로 다양하게 활용될 수 있으며, 특히 최 근 사회문제가 되고 있는 폐광지역 주민들의 식수 안전문제에도 많은 도움을 줄 수 있을 것이다. According to the present invention, heavy metals that may be included in soft drinks, green juice, beverages, herbal medicines, etc. can be easily and effectively removed using a tea bag containing the adsorbent beads of the present invention, and in particular, four heavy metals regulated by Chinese herbal medicines (lead, cadmium, Mercury and arsenic) also show excellent removal performance. The adsorbent of the present invention not only consists of ingredients beneficial to humans but also possesses high antibacterial performance, so that it can be used in various fields in the food field where safety is important in addition to herbal medicines. It will be able to help residents' drinking water safety issues.

Claims (3)

a)초산 용액으로 키토산을 용해시킨 후 인산 용액과 혼합하여 키토산/인산 혼합액을 제조하는 공정, b)얻어진 키토산/인산 혼합액을 수산화칼슘 현탁액에 적하시켜 수산화아파타이트를 합성하는 공정, c)얻어진 키토산/수산화아파타이트 복합체를 증류수로 수세한 후 압착탈수하고 몰드에서 성형한 후 건조시키는 공정으로 이루어지는 것을 특징으로 하는 천연물질 유래 중금속 흡착제의 제조방법.a) dissolving chitosan in acetic acid solution and mixing with phosphoric acid solution to prepare a chitosan / phosphate mixture, b) dropping the obtained chitosan / phosphate mixture into a calcium hydroxide suspension to synthesize apatite, c) obtained chitosan / hydroxyl A method for producing a heavy metal adsorbent derived from natural materials, comprising a step of washing an apatite complex with distilled water, followed by compression and dehydration, molding in a mold, and drying. 제 1 항에 있어서, 상기 a)공정이후 키토산/인산 혼합액을 동결건조한 후 폴리카르복시산을 첨가하는 공정을 포함하는 것을 특징으로 하는 천연물질 유래 중금속 흡착제의 제조방법. 2. The method of claim 1, further comprising a step of lyophilizing the chitosan / phosphate mixture after the step a) followed by adding polycarboxylic acid. 제1항 또는 제2항의 제조방법에 의해 제조된 키토산/수산화아파타이트 복합체로 이루어진 천연물질 유래 중금속 흡착제.A heavy metal adsorbent derived from natural substances consisting of chitosan / hydroxyapatite composites prepared by the process according to claim 1 or 2.
KR1020050068708A 2005-07-28 2005-07-28 The precipitation of heavy metal adsorbant derived from natural materials and the product thereof KR20070014260A (en)

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