JPH0651114B2 - Chitosan-magnetic composite particles and method for producing the same - Google Patents
Chitosan-magnetic composite particles and method for producing the sameInfo
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- JPH0651114B2 JPH0651114B2 JP2079989A JP7998990A JPH0651114B2 JP H0651114 B2 JPH0651114 B2 JP H0651114B2 JP 2079989 A JP2079989 A JP 2079989A JP 7998990 A JP7998990 A JP 7998990A JP H0651114 B2 JPH0651114 B2 JP H0651114B2
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は、良好な機械的強度を有し、かつ磁場を印加す
ることにより簡単に分離回収に行いうる、吸着剤として
好適なキトサン−磁性体複合粒子及びその製造方法に関
するものである。TECHNICAL FIELD The present invention relates to a chitosan-magnetic material composite suitable as an adsorbent which has good mechanical strength and can be easily separated and recovered by applying a magnetic field. The present invention relates to particles and a method for producing the particles.
従来の技術 キトサンは、他の物質に対し、良好な吸着性を示すた
め、タンパク質の分別精製用、イオン交換用、重金属イ
オンの分離用などの吸着剤として広く用いられている。2. Description of the Related Art Chitosan has been widely used as an adsorbent for fractionating and purifying proteins, for ion exchange, for separating heavy metal ions, etc. because it exhibits good adsorbability to other substances.
ところで、このようなキトサン系吸着剤としては、これ
まで粉末キトサンを塩基性溶液中に懸濁し、エピクロロ
ヒドリンにより架橋させたもの（「工業化学雑誌」、第
68巻、第904頁）、キトサン溶液を中性又は塩基性溶液
で凝固させて得た多孔質キトサンを、有機ジイソシアネ
ートで架橋させたもの（特開昭61-133143号公報）、キ
トサン溶液を中性又は塩基性溶液中に滴下してキトサン
粒状体を形成させ、次いで、これをN−アセチル化した
のち架橋し、さらに脱アセチル化したもの（特開昭62-7
0401号公報）などが知られている。By the way, as such a chitosan-based adsorbent, one obtained by suspending powdered chitosan in a basic solution and then crosslinked with epichlorohydrin (“Industrial Chemistry Magazine”, No. 1).
68, p. 904), porous chitosan obtained by coagulating a chitosan solution with a neutral or basic solution, cross-linked with an organic diisocyanate (JP-A 61-133143), and a chitosan solution A chitosan granule is formed by dropping it into a basic or basic solution, which is then N-acetylated, crosslinked, and then deacetylated (JP-A-62-7).
No. 0401) is known.
しかし、これらのキトサン系吸着剤は、酸性溶液又は塩
基性溶液中で膨潤しやすいし、また、機械的強度が低い
ため、取り扱いにくい上に、使用後の分離が困難で利用
範囲が制限されるという欠点があった。However, these chitosan-based adsorbents are easily swelled in an acidic solution or a basic solution, and have low mechanical strength. Therefore, they are difficult to handle, and separation after use is difficult, which limits their use range. There was a drawback.
発明が解決しようとする課題 本発明は、このような従来のキトサン系吸着剤のもつ欠
点を克服し、良好な機械的強度を有し、取り扱いやすい
上に、溶液状として使用可能で耐久性に優れ、しかも使
用後の分離が容易で、良好な吸着能を有する新規なキト
サン系複合体を提供することを目的としてなされたもの
である。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention overcomes the drawbacks of the conventional chitosan-based adsorbents, has good mechanical strength, is easy to handle, and can be used as a solution to provide durability. The object of the present invention is to provide a novel chitosan-based complex which is excellent, easy to separate after use, and has good adsorption ability.
課題を解決するための手段 本発明者らは、優れた性質をもち、吸着剤として有用な
新規なキトサン系複合体を開発するために種々研究を重
ねた結果、架橋化キトサン粒状体中に複数の磁性微粒子
を内包させることにより、その目的を達成しうことを見
い出し、この知見に基づいて本発明を完成するに至っ
た。Means for Solving the Problems The inventors of the present invention have conducted various studies to develop a novel chitosan-based composite having excellent properties and useful as an adsorbent, and as a result, a plurality of chitosan-based particles in a crosslinked chitosan granule were obtained. It was found that the object of the invention can be achieved by including the magnetic fine particles of (3), and the present invention has been completed based on this finding.
すなわち、本発明は、架橋化キトサン粒状体とその中に
内包された複数の磁性微粒子とから成るキトサン−磁性
体複合粒子を提供するものである。That is, the present invention provides chitosan-magnetic composite particles composed of a crosslinked chitosan granular material and a plurality of magnetic fine particles contained therein.
このようなキトサン−磁性体複合粒子は、先ずキトサン
の酸性溶液中に磁性微粒子を分散させたのち、次にこの
溶液を中性又は塩基性に変えるか、あるいはこの溶液を
塩基性溶液中に滴下しかきまぜることにより、複数の磁
性微粒子を内包したキトサン粒状体を生成させ、次いで
キトサンの架橋化を行うことにより製造することができ
る。Such chitosan-magnetic composite particles are prepared by first dispersing magnetic fine particles in an acidic solution of chitosan, and then changing the solution to neutral or basic, or dropping the solution into a basic solution. It can be manufactured by forming chitosan granules containing a plurality of magnetic fine particles by stirring and then crosslinking the chitosan.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明において、架橋化キトサンはキトサンをそのグル
コサミン残基等において架橋剤等で架橋化して得られる
ものである。キトサンは特に制限されず、通常キチンを
脱アセチル化して得られ、その反応条件によって得られ
るキトサンの性質は異なるが、いずれのものでもよい。In the present invention, the crosslinked chitosan is obtained by crosslinking chitosan at its glucosamine residue or the like with a crosslinking agent or the like. Chitosan is not particularly limited and is usually obtained by deacetylating chitin, and the properties of chitosan obtained differ depending on the reaction conditions, but any may be used.
架橋化キトサンにより被覆される磁性微粒子は特に制限
されず、例えばマグネタイト、ヘマタイト、フェライ
ト、鉄などが用いられる。その粒径は通常１０μ以下で
ある。この磁性微粒子の含有割合は、使用するキトサン
の種類、濃度、分散状態等によって適宜選択される。The magnetic fine particles coated with the crosslinked chitosan are not particularly limited and, for example, magnetite, hematite, ferrite, iron and the like are used. The particle size is usually 10 μ or less. The content ratio of the magnetic fine particles is appropriately selected depending on the type, concentration, dispersion state and the like of chitosan used.
本発明のキトサン−磁性体複合粒子を製造するには、キ
トサンを塩酸のような無機酸、スルファミン酸、ギ酸、
酢酸、乳酸、リンゴ酸のような有機酸などの酸性物質の
単独又は混合物と水性媒体、好ましくは水より成る溶液
に溶解し、キトサン酸性溶液を調製する。キトサンの濃
度はその種類によって異なるが、通常は２％以下であ
る。このキトサン溶液に磁性微粒子を分散させたのち、
この溶液を、それに塩基性物質を例えば水溶液のような
溶液として適当量添加し、中性又は塩基性に変えるか、
あるいはこの塩基性物質を含む溶液中に滴下しかきまぜ
ることにより、複数の磁性微粒子を内包したキトサン粒
状体を生成させる。この塩基性物質としては、例えばNaO
H、KOH、Na2CO3、アンモニア、エチレンジアミンなどを
挙げることができる。また、水溶液の場合にはメタノー
ル、エタノールのようなアルコールを加えてもよい。磁
性微粒子はキトサン酸性溶液によく分散させた状態とし
て、これに塩基性物質の溶液と接触させるのが好ましい
ので、キトサン酸性溶液中への塩基性物質溶液の添加あ
るいは塩基性物質溶液中へのキトサン酸性溶液の滴下は
通常かきまぜや振りまぜしながら行われる。In order to produce the chitosan-magnetic composite particles of the present invention, chitosan is used as an inorganic acid such as hydrochloric acid, sulfamic acid, formic acid,
An acidic solution of chitosan is prepared by dissolving an acidic substance such as acetic acid, lactic acid or an organic acid such as malic acid alone or in a mixture with an aqueous medium, preferably water. The concentration of chitosan varies depending on its type, but is usually 2% or less. After dispersing magnetic particles in this chitosan solution,
To this solution, a basic substance is added thereto in an appropriate amount as a solution such as an aqueous solution to change the solution to neutral or basic, or
Alternatively, a chitosan granule containing a plurality of magnetic fine particles is produced by dropping and stirring in a solution containing the basic substance. Examples of this basic substance include NaO
H, KOH, Na 2 CO 3 , ammonia, ethylenediamine and the like can be mentioned. Further, in the case of an aqueous solution, alcohol such as methanol or ethanol may be added. Since it is preferable that the magnetic fine particles are well dispersed in an acidic chitosan solution and then brought into contact with a solution of a basic substance, addition of the basic substance solution to the acidic chitosan solution or chitosan to the basic substance solution. The dropping of the acidic solution is usually performed while stirring or shaking.
次に、このようにして得られる磁性微粒子内包キトサン
粒状体を架橋化させるが、この反応は、通常は架橋剤を
用いて極性溶媒中で行われる。この際に用いられる架橋
剤としては、例えばエピクロロヒドリン、2,3−ジクロ
ロプロパノール、1−クロロ−2,3−エピチオプロパン、
ヘキサメチレンジイソシアネートなどを挙げることがで
きる。架橋剤の使用量は、通常はキトサンのグルコサミ
ン残基１モル対し、０．５〜１０モルの範囲で選ばれ
る。Next, the magnetic fine particle-encapsulated chitosan granules thus obtained are crosslinked, and this reaction is usually carried out in a polar solvent using a crosslinking agent. Examples of the crosslinking agent used at this time include epichlorohydrin, 2,3-dichloropropanol, 1-chloro-2,3-epithiopropane,
Hexamethylene diisocyanate and the like can be mentioned. The amount of the cross-linking agent used is usually selected in the range of 0.5 to 10 mol with respect to 1 mol of the glucosamine residue of chitosan.
架橋化反応後、その生成物は、それを収容する容器等の
外部から磁場をかけて吸引し、溶媒等を分離して洗浄を
繰り返し精製し、所望濃度のキトサン−磁性体複合粒子
分散溶液を得ることができる。After the cross-linking reaction, the product is suctioned by applying a magnetic field from the outside of a container or the like that contains it, and the solvent and the like are separated and washed repeatedly to obtain a chitosan-magnetic composite particle dispersion solution having a desired concentration. Obtainable.
発明の効果 本発明のキトサン−磁性体複合粒子は、キトサン粒子中
に磁性微粒子を内包しているため、溶液中に分散させて
吸着処理を行った後、外部から磁場をかけることによ
り、簡単に分離、回収を行うことができる。この磁気分
離法によれば、磁性微粒子内包キトサンの粒子を極めて
小さくすることが可能で、これにより表面積を著しく増
大させ、キトサン単位重量当りの吸着速度を高め、粒子
内部拡散も容易に行える。Advantageous Effects of Invention The chitosan-magnetic composite particles of the present invention include magnetic fine particles in chitosan particles, and therefore, after being dispersed in a solution and subjected to an adsorption treatment, by applying a magnetic field from the outside, it is easy. Separation and recovery can be performed. According to this magnetic separation method, it is possible to make the particles of the magnetic fine particle-encapsulated chitosan extremely small, thereby significantly increasing the surface area, increasing the adsorption rate per unit weight of chitosan, and easily diffusing inside the particles.
また、本発明のキトサン−磁性体複合粒子は、良好な機
械的強度を有し、取り扱いやすい上に、溶液中に分散さ
せて使用しうるため、キトサンに対して外部から大きな
物理的力が加わらず、従来のキトサン系吸着剤と比べて
より長期間使用することができるという利点もある。Further, the chitosan-magnetic composite particles of the present invention have good mechanical strength, are easy to handle, and can be used by being dispersed in a solution. Therefore, a large physical force is applied to chitosan from the outside. In addition, there is an advantage that it can be used for a longer period of time as compared with the conventional chitosan-based adsorbent.
さらに、本発明方法は、磁性微粒子を分散させたキトサ
ン溶液に塩基性溶液を加えた後、架橋化させるという簡
便な方法であって、洗浄等の処理ではろ過、遠心分離等
の煩雑な操作を必要とせず、キトサン−磁性体複合粒子
に磁場を印加する、例えば磁石で吸引するだけで容易に
回収分離することができるので、工業的に有利に利用し
うる。Furthermore, the method of the present invention is a simple method of crosslinking after adding a basic solution to a chitosan solution in which magnetic fine particles are dispersed, and in treatment such as washing, complicated operations such as filtration and centrifugation are performed. It is not necessary and can be easily recovered and separated by applying a magnetic field to the chitosan-magnetic composite particles, for example, only by attracting with a magnet, so that it can be industrially advantageously utilized.
実施例 次に、実施例によって本発明をさらに詳細に説明する。EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
キトサン−磁性体複合粒子分散溶液を資料として、その
収量、陰イオン交換容量及び磁性微粒子含有率を次のと
おり求めた。Using the chitosan-magnetic composite particle dispersion solution as a reference, its yield, anion exchange capacity and magnetic fine particle content were determined as follows.
(１)収量 資料ｗ1(g)からｗ2(g)を秤取し、蒸発乾固して乾燥重量
ｗ3(g)を求め、次式により算出した。(1) Yield W 2 (g) was weighed from data w 1 (g), evaporated to dryness to obtain dry weight w 3 (g), and calculated by the following formula.
(２)陰イオン交換容量 前記試料からｗ4(g)を秤取し、0.1N HCl 10mlを加えて
２５℃で１時間かきまぜて、0.1N NaOHでメチルレッド
を指示薬として滴定し、次式により吸着された塩基イオ
ン量を求めて算出した。 (2) Anion exchange capacity w 4 (g) was weighed out from the above sample, added with 10 ml of 0.1N HCl, stirred at 25 ° C. for 1 hour, and titrated with methyl red as an indicator with 0.1N NaOH. The amount of adsorbed base ions was calculated and calculated.
（ここで、ａ：0.1N NaOH消費量、 fHCl：0.1N HClの力価 fNoOH：0.1N NaOHの力価 である） (３)磁性微粒子含有率 前記試料を乾燥したキトサン−磁性体複合粒子の磁性微
粒子含有率は、重量法、元素分析装置、示差熱分析装置
により測定した。 (Here, a: 0.1N NaOH consumption, f HCl : 0.1N HCl titer f NoOH : 0.1N NaOH titer) (3) Magnetic fine particle content rate Chitosan-magnetic substance composite obtained by drying the sample The magnetic fine particle content of the particles was measured by a gravimetric method, an elemental analyzer, and a differential thermal analyzer.
実施例１〜８ 脱アセチル化度87.7％のキトサン0.225gを0.005規定塩
酸300mlに溶解し、7.5gのマグネタイト（平均粒径0.5、
比表面積５m2／g）を加え分散させたのち、600rpmでよ
くかきまぜながら１規定NaOH１５mlを徐々に滴下し、さ
らにエピクロロヒドリン0.129gを加えて加熱し、２時間
煮沸還流した。反応物を0.1N HCl、0.1N NaOH、脱イオ
ン水でよく洗い、磁石で容器の底部に引き付けてから上
澄みを取り除き、キトサン−磁性体複合粒子分散溶液を
得た。Examples 1 to 8 0.225 g of chitosan having a deacetylation degree of 87.7% was dissolved in 300 ml of 0.005N hydrochloric acid, and 7.5 g of magnetite (average particle size 0.5,
A specific surface area of 5 m 2 / g) was added and dispersed, 15 ml of 1N NaOH was gradually added dropwise while stirring well at 600 rpm, 0.129 g of epichlorohydrin was further added, and the mixture was heated and boiled under reflux for 2 hours. The reaction product was thoroughly washed with 0.1N HCl, 0.1N NaOH and deionized water, attracted to the bottom of the container with a magnet, and the supernatant was removed to obtain a chitosan-magnetic composite particle dispersion solution.
次に、マグネタイト又はエピクロロヒドリンあるいはそ
の両方の所要量を変えたこと以外は、上記方法と同様に
してキトサン−磁性体複合粒子分散溶液を得た。Next, a chitosan-magnetic composite particle-dispersed solution was obtained in the same manner as the above method except that the required amounts of magnetite and / or epichlorohydrin were changed.
以上の試料について、収量及び乾燥重量当りの陰イオン
交換容量を求めた。その結果を次表に示す。The yield and anion exchange capacity per dry weight of the above samples were determined. The results are shown in the table below.
いずれの生成物も酸性、中性、塩基性溶液中で容易に磁
気分離された。また、顕微鏡観察によりマグネタイト微
粒子がキトサンゲル中に均一に内包されていることが確
認された。 Both products were easily magnetically separated in acidic, neutral and basic solutions. Further, it was confirmed by microscopic observation that the magnetite fine particles were uniformly encapsulated in the chitosan gel.
比較例 脱アセチル化度87.7％のキトサン0.225gを0.005N HCl 3
00mlに溶解させ、600rpmで分散させたのち、600rpmでよ
くかきまぜながらエピクロロヒドリン0.129gを加えて加
熱し、２時間煮沸還流したところ、反応物は微細なゲル
粒子となり、洗浄後、ろ過あるいは遠心分離法により溶
液から分離できなかった。Comparative Example 0.225 g of chitosan with a degree of deacetylation of 87.7% was added to 0.005 N HCl 3
After dissolving in 00 ml and dispersing at 600 rpm, 0.129 g of epichlorohydrin was added while stirring well at 600 rpm and heated, and the mixture was boiled under reflux for 2 hours, the reaction product became fine gel particles, and after washing, filtration or It could not be separated from the solution by centrifugation.
実施例９ 脱アセチル化度81.9％のキトサン0.225gを0.01N HCl 30
0mlに溶解させ、0.1gのヘマタイト(平均粒径0.5μ、比
表面積５m2／g)を加え分散させたのち、600rpmでよくか
きまぜながら１N NaOH１５mlを徐々に滴下し、さらにエ
ピクロロヒドリン0.129gを加えて加熱し、２時間煮沸還
流したのち、実施例１と同様の操作を行ってキトサン−
磁性体複合粒子分散溶液を得た。その収量及び乾燥重量
当りの陰イオン交換容量はそれぞれ0.30g及び1.701meq
／gであった。Example 9 0.225 g of chitosan having a degree of deacetylation of 81.9% was added to 0.01 N HCl 30
Dissolve in 0 ml, add 0.1 g of hematite (average particle size 0.5 μ, specific surface area 5 m 2 / g) and disperse, then slowly add 15 ml of 1N NaOH while stirring well at 600 rpm, and then add 0.129 g of epichlorohydrin. Was added and heated, and the mixture was boiled under reflux for 2 hours. Then, the same operation as in Example 1 was performed to carry out chitosan-
A magnetic substance composite particle dispersion solution was obtained. The yield and anion exchange capacity per dry weight are 0.30 g and 1.701 meq, respectively.
It was / g.
生成物の磁気分離は容易に行われ、微粒子の内包状態も
良好であった。Magnetic separation of the product was easily performed, and the state of inclusion of fine particles was also good.
実施例１０ 脱アセチル化度87.7％のキトサン0.30gを0.005 N HCl 3
00mlに溶解させ、0.1gのバリウムフェライト(平均粒径
1.2μ、比表面積1.5m2／g)を加え分散させたのち、600r
mpでよくかきまぜながら１N NaOH 15mlを徐々に滴下し、
さらにエピクロロヒドリン0.645gを加えて加熱し、２時
間煮沸還流したのち、実施例１と同様の操作を行ってキ
トサン−磁性体複合粒子分散溶液を得た。その収量及び
乾燥重量当りの陰イオン交換容量はそれぞれ0.41g及び
2.25meq／gであった。Example 10 0.30 g of chitosan having a deacetylation degree of 87.7% was added to 0.005 N HCl 3
Dissolve in 00 ml, 0.1 g barium ferrite (average particle size
1.2μ, specific surface area 1.5m 2 / g) and disperse, then 600r
While stirring well with mp, gradually add 15 ml of 1N NaOH,
Furthermore, 0.645 g of epichlorohydrin was added and heated, and after boiling and refluxing for 2 hours, the same operation as in Example 1 was performed to obtain a chitosan-magnetic composite particle dispersion solution. Its yield and anion exchange capacity per dry weight were 0.41 g and
It was 2.25 meq / g.
生成物の磁気分離は容易に行われ、微粒子の内包状態も
良好であった。Magnetic separation of the product was easily performed, and the state of inclusion of fine particles was also good.
実施例１１ アセチル化度87.7％のキトサン0.225gを0.01 N HCl 300
mlに溶解させ、0.1gのマグネタイト(平均粒径0.8μ、比
表面積２m2／g）を加え分散させたのち、600rmpでよく
かきまぜながら１N NaOH 15mlを徐々に滴下した。次い
で、希塩酸、希水酸化ナトリウム、脱イオン水で洗浄し
たのち、磁気分離し、さらにアセトン中でかきまぜ、水
分をアセトンで完全に置換除去した。次いで、ヘキサメ
チレンジイソシアネート0.235gを含む溶液中でかきまぜ
ながら３０℃で２時間反応させ、キトサン−磁性体複合
粒子分散溶液0.38gを得た。Example 11 0.225 g of chitosan having a degree of acetylation of 87.7% was added to 0.01 N HCl 300
After dissolving in 0.1 ml of magnetite and adding 0.1 g of magnetite (average particle size: 0.8 μ, specific surface area: 2 m 2 / g) to disperse the mixture, 15 ml of 1N NaOH was gradually added dropwise while thoroughly stirring at 600 rpm. Then, after washing with dilute hydrochloric acid, dilute sodium hydroxide, and deionized water, magnetic separation was performed, and the mixture was stirred in acetone to completely replace water with acetone for removal. Then, the mixture was reacted in a solution containing 0.235 g of hexamethylene diisocyanate with stirring at 30 ° C. for 2 hours to obtain 0.38 g of a dispersion solution of chitosan-magnetic material composite particles.
このものを水銀、カドミウムイオン１ppmを含む溶液に
分散させ、磁気分離したところ、溶液中には水銀、カド
ミウムが検出されなかった。When this was dispersed in a solution containing 1 ppm of mercury and cadmium ions and magnetically separated, mercury and cadmium were not detected in the solution.
Claims (3)
た複数の磁性微粒子とから成るキトサン−磁性体複合粒
子。1. Chitosan-magnetic composite particles comprising a crosslinked chitosan granular material and a plurality of magnetic fine particles contained therein.
させたのち、この溶液を中性又は塩基性に変えることに
より複数の磁性微粒子を内包したキトサン粒状体を生成
させ、次いでキトサンの架橋化を行うことを特徴とする
請求項１記載のキトサン−磁性体複合粒子の製造方法。2. Magnetic particles are dispersed in an acidic solution of chitosan, and the solution is changed to neutral or basic to produce chitosan granules containing a plurality of magnetic particles, and then chitosan is crosslinked. The method for producing chitosan-magnetic composite particles according to claim 1, wherein
させたのち、この溶液を塩基性溶液中に滴下し、かきま
ぜることにより複数の磁性微粒子を内包したキトサン粒
状体を生成させ、次いでキトサンの架橋化を行うことを
特徴とする請求項１記載のキトサン−磁性体複合粒子の
製造方法。3. Dispersing magnetic fine particles in an acidic solution of chitosan, dropping this solution into a basic solution, and stirring the mixture to form chitosan granules containing a plurality of magnetic fine particles. The method for producing chitosan-magnetic composite particles according to claim 1, wherein crosslinking is performed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2079989A JPH0651114B2 (en) | 1990-03-28 | 1990-03-28 | Chitosan-magnetic composite particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2079989A JPH0651114B2 (en) | 1990-03-28 | 1990-03-28 | Chitosan-magnetic composite particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03278834A JPH03278834A (en) | 1991-12-10 |
| JPH0651114B2 true JPH0651114B2 (en) | 1994-07-06 |
Family
ID=13705720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2079989A Expired - Lifetime JPH0651114B2 (en) | 1990-03-28 | 1990-03-28 | Chitosan-magnetic composite particles and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0651114B2 (en) |
Cited By (1)
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|---|---|---|---|---|
| CN105170103A (en) * | 2015-09-25 | 2015-12-23 | 哈尔滨工程大学 | Furfural-modified crosslinked-chitosan chelate resin magnetic particles and preparation method |
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|---|---|---|---|---|
| JP2005296942A (en) * | 2004-03-15 | 2005-10-27 | Hitachi Maxell Ltd | Magnetic composite particle and method for producing it |
| JP4831313B2 (en) * | 2006-01-18 | 2011-12-07 | 富士紡ホールディングス株式会社 | Carrier for immobilizing chitosan-based microorganisms having magnetism and method for producing the same |
| JP5489033B2 (en) * | 2009-05-11 | 2014-05-14 | 国立大学法人 宮崎大学 | Method for recovering oxoanions such as molybdenum, tungsten and vanadium with cross-linked chitosan starting from chitin |
| CN101940914A (en) * | 2010-09-27 | 2011-01-12 | 宁波天韵生态治理工程有限公司 | Method for producing adsorbent by using polyphosphoric sodium phosphate-coupled chitosan and bamboo charcoal |
| CN103406101B (en) * | 2013-07-08 | 2015-05-20 | 西北农林科技大学 | Preparation of dye-philic magnetic microsphere and application of dye-philic magnetic microsphere in separation of lactoferrin in whey |
| CN103521192B (en) * | 2013-10-15 | 2015-08-26 | 台州学院 | A kind of magnetic biological adsorption agent for the treatment of dyeing waste water and preparation method thereof |
| CN104549162B (en) * | 2014-11-04 | 2017-01-25 | 华文蔚 | Preparation method of stationary phase of magnetic fluidized bed for separating chiral substances |
| CN113061595A (en) * | 2021-03-17 | 2021-07-02 | 东北农业大学 | Method for immobilizing phospholipase C by using epoxy group modified magnetic chitosan nanoparticles as carrier |
| CN113413880A (en) * | 2021-06-07 | 2021-09-21 | 中南大学 | Preparation and application of thermal-modification-based chitosan-coated iron-manganese mineral material |
| CN115337912A (en) * | 2022-08-03 | 2022-11-15 | 河池学院 | Magnetic cross-linked chitosan-polyethyleneimine/biochar composite gel particles and preparation method thereof |
-
1990
- 1990-03-28 JP JP2079989A patent/JPH0651114B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170103A (en) * | 2015-09-25 | 2015-12-23 | 哈尔滨工程大学 | Furfural-modified crosslinked-chitosan chelate resin magnetic particles and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03278834A (en) | 1991-12-10 |
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