JPS5870835A - Adsorptive removal of polar org. compound - Google Patents

Adsorptive removal of polar org. compound

Info

Publication number
JPS5870835A
JPS5870835A JP16773681A JP16773681A JPS5870835A JP S5870835 A JPS5870835 A JP S5870835A JP 16773681 A JP16773681 A JP 16773681A JP 16773681 A JP16773681 A JP 16773681A JP S5870835 A JPS5870835 A JP S5870835A
Authority
JP
Japan
Prior art keywords
compound
polar
org
polar organic
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP16773681A
Other languages
Japanese (ja)
Inventor
Yasuo Takenaka
竹中 安夫
Tomihiko Kawamura
川村 富彦
Shuichi Sugimori
杉森 修一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Priority to JP16773681A priority Critical patent/JPS5870835A/en
Publication of JPS5870835A publication Critical patent/JPS5870835A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To adsorb and remove a polar org. compound rapidly and effectively, by contacting a solution containing the polar org. compound having an ionizable group with titanium dioxide hydrate. CONSTITUTION:A solution containing an org. compound having an ionizable group such as a carboxyl group or a sulfonic acid group such as various fatty acids or alkylbenzene sulfonic acid is contacted with titanium dioxide hydrate prepared by hydrolysis of titanyl sulfate or titanium tetrapropoxide. By this method, the polar org. compound can be adsorbed and removed rapidly and effectively without applying any pretreatment.

Description

【発明の詳細な説明】 本発明は極性有機化合物特に電離基を有する極性有機化
合物を含む溶液から何ら前処理を施すことなく極性有機
化合物を迅速かつ効果的に吸着・除去する簡便な方法に
関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a simple method for quickly and effectively adsorbing and removing polar organic compounds from a solution containing polar organic compounds, particularly polar organic compounds having ionizable groups, without any pretreatment. It is.

生活廃水や生化学的物質を含有する溶液等は多極多様な
有機化合物の共存する溶液でありこれらの中に微量に存
在する非極性化合物を分離するに際しては共存極性化合
物の影響を避けることが困難である。
Domestic wastewater and solutions containing biochemical substances are solutions in which a large number of diverse organic compounds coexist, and when separating trace amounts of nonpolar compounds present in these solutions, it is necessary to avoid the effects of coexisting polar compounds. Have difficulty.

たとえば、このような非極性′4#機化合物をガスク四
マドグラブを用いて分析しようとすると極性成分やタン
パク質等の高分子量成分がカラムにg!に71すること
に基くカラムの劣化や理論段数の低下、定性、定量分析
における再現性の不良−さらに検出器に付着することに
よるノイズの発生、感度の低下等の不都合1招く□また
、液体クロマトグラフ分析に際しては1極性および非極
性化合物を同時に分析するカラム条件の設定は困難であ
り、通常それぞれに最適の条件を設定してコ権以上の条
件を順次実施する等複雑な操作を必要とする。
For example, when trying to analyze such a non-polar 4# compound using a Gask 4Mad grab, polar components and high molecular weight components such as proteins are deposited on the column. Column deterioration, reduction in the number of theoretical plates, and poor reproducibility in qualitative and quantitative analysis due to 71 - In addition, adhesion to the detector may cause noise generation, reduced sensitivity, and other inconveniences. When performing graph analysis, it is difficult to set column conditions for simultaneous analysis of monopolar and non-polar compounds, and usually requires complex operations such as setting the optimal conditions for each and sequentially implementing more than one set of conditions. .

さらに血液や尿等の体液中の非極性化合物を分析する必
要のある臨床化学分析においては体液中に最も多量に存
゛在するタンパク質を除失しておくことが胤ましい。た
とえば体液の代表である血清に呈色試薬を添加するとほ
とんどの例で混濁を生じ、比色測定は不可能となるから
である□丁なわち分析の第一歩として除タンパク操作と
いう煩雑な前処理が従来必須とされたが分析操作に迅速
性を欠くことのできない条件とする臨床化学分析におい
てはこの前処理操作に長時間を要することは許されない
Furthermore, in clinical chemistry analysis where it is necessary to analyze nonpolar compounds in body fluids such as blood and urine, it is critical to remove proteins that are present in the greatest amount in body fluids. For example, when a coloring reagent is added to serum, which is a representative body fluid, it becomes cloudy in most cases, making colorimetric measurements impossible. Conventionally, processing has been considered essential, but in clinical chemical analysis, where speed is an essential condition for analytical operations, it is unacceptable for this pretreatment operation to take a long time.

従来、タンパク質や酵素等の極性化合物の除失には除タ
ンパク試薬を用いる前処理法、透析膜法、電気泳動法等
が知られているが、これらはいずれも精密な分離法では
あるが操作が仮錨で長時間を要するものである。
Conventionally, methods known for removing polar compounds such as proteins and enzymes include a pretreatment method using a protein removal reagent, a dialysis membrane method, and an electrophoresis method.Although these methods are all precise separation methods, they require manual operation. This is a temporary anchor and takes a long time.

本発明者らはかかる従来法の欠点を軽減し取り扱いが容
易で迅速な烏分子量および低分子蓋極性化合物の除去方
法を確立する目的で検討を重ねた結果本発明を完成する
に致った。
The present inventors have completed the present invention as a result of repeated studies aimed at alleviating the drawbacks of the conventional methods and establishing a method for removing the low-molecular-weight and low-molecular-weight polar compounds that is easy and quick to handle.

すなわち本発明はm、m基を有する極性有機化合物を含
む溶液を二酸化チタン水和物(以下チタン酸、と略す)
に接触させ、該極性有機化合物を吸着除去させる方法で
ある。
That is, the present invention converts a solution containing a polar organic compound having m and m groups into titanium dioxide hydrate (hereinafter abbreviated as titanic acid).
This is a method in which the polar organic compound is adsorbed and removed by contacting with the organic compound.

本発明に言う電離基を有する極性有機化合物とは一、浴
猷中で解離して陽イオン又は陰イオンを有することの出
来る電離基を有する有機化合物である。このよりな′v
IL離基としては1カルボキシル&(−COOH)、ス
、ルホン酸基(80,H)、ホスホン基(PO,H,)
  等が電離して陰イオンをもつ基として、また第一ア
ミン、第二アミン、第三アミン基等は、溶液中で水素イ
オンと結合し、陽イオンをもつ基として挙げられるot
たアルカリ金属塩や塩酸塩等のこれら電離基に結合した
塩類も本発明で言う電離基に含まれる〇これらの電離基
を有する極性有機化合物としては酢飯等の各種脂肪酸、
アルキルベンゼンスルホン酸、リン脂質、各種アミ/@
、蛋白質、酵素等が本発明の方法で除去出来る0特にア
ミノ酸Sgi白質、酵素等でカルボキシル基とアミ7基
(NH,)の両電離基を有している極性Tll1/A化
合物が本発明の方法で効果的に除失す・ることが出来る
The polar organic compound having an ionizable group as used in the present invention is an organic compound having an ionizable group that can be dissociated in a bath to form a cation or an anion. This way'v
IL leaving groups include 1 carboxyl & (-COOH), su, sulfonic acid group (80, H), phosphonic group (PO, H,)
etc. as groups that ionize and have anions, and primary amine, secondary amine, tertiary amine groups, etc. as groups that combine with hydrogen ions and have cations in solution.
Salts bonded to these ionized groups, such as alkali metal salts and hydrochlorides, are also included in the ionized groups referred to in the present invention.Polar organic compounds having these ionized groups include various fatty acids such as vinegared rice,
Alkylbenzenesulfonic acids, phospholipids, various amino acids/@
, proteins, enzymes, etc. can be removed by the method of the present invention. In particular, polar Tll1/A compounds having both a carboxyl group and an amine group (NH, ) in white matter, enzymes, etc., can be removed by the method of the present invention. It can be effectively removed using this method.

次に本発明で、用いられるチタン酸とは化学式%式% 化チタン水和物であるが、硫酸チタニル(T10804
)、チタンテトライソプロポキシド(Ti(OCR(C
Hm)t )a ) 、四塩化チタン(TiC)−等の
加水分解によって製造されたものであれば比表面積が大
きく吸着の目的のためには好都合である。
Next, in the present invention, the titanic acid used is titanium hydrate with the chemical formula %, and titanyl sulfate (T10804
), titanium tetraisopropoxide (Ti(OCR(C
Hm)t)a), titanium tetrachloride (TiC), etc., which are produced by hydrolysis, have a large specific surface area and are convenient for the purpose of adsorption.

さらに、特開t5kk−Kg亭亭号明細警に開示されて
いるような方法で製造したチタン酸が好ましい。即ちア
ナターゼ形もしくは無定形の結晶構造を有するチタンの
水和化合物に無機酸及び水を混合し、混線、押し出し造
粒した後乾燥したものは形態安定性に優れ好ましいチタ
ン#I吸着剤となる〇 特に、上記方法で造粒−成形された粒状物あるいはこれ
を粉砕1篩分した整粒物であるならばカートリッジ等に
充填して使用するに際しても操作性において有利である
。粒状物の粒径はgoNioooμであれば好ましいが
、100〜S00μであればより好ましく、iso〜亭
OQμであればカラム等への充填便用に対し最適である
Further preferred is titanic acid produced by the method disclosed in Japanese Patent Application Laid-Open No. 2003-120002. In other words, a hydrated titanium compound having an anatase or amorphous crystal structure mixed with an inorganic acid and water, mixed, extruded, granulated, and dried becomes a preferred titanium #I adsorbent with excellent morphological stability. Particularly, if the granules are granulated and molded by the above-mentioned method or are sized by pulverizing and sieving the granules, they are advantageous in terms of operability when used by filling them into cartridges and the like. The particle size of the granules is preferably goNioooμ, more preferably 100 to S00μ, and iso to OQμ optimal for use in packing into columns and the like.

次に本発明の方法を図面を用いて具体的に説明する。円
筒状小力ラム(お内に上記チタン酸(すを元塙する。カ
ラムの形状は任意であるが円筒状が扱い易い。また大き
さは試料濃度や試料量に応じて定めればよいが、試料s
〜10m1に対してチタン酸lN−りとするのが適当で
ある。
Next, the method of the present invention will be specifically explained using the drawings. A small cylindrical column (inside the titanic acid).The shape of the column can be arbitrary, but a cylindrical shape is easy to handle.Also, the size can be determined depending on the sample concentration and sample amount. , sample s
It is appropriate to use lN-titanic acid for ~10 ml.

カラムの材質は試料を変性させるものでなければ何でも
よいが、ガラスかステンレススチールであれは十分な強
度を有する。このカラムの両端にフィルター(3)付き
の出入口(6)、(7)を設け、一方は試料の入口とし
て〜例えばシリンジ(1)により試料浴液(コ)を供給
し、他方は処理液の出口ζする。フィルター(3)はチ
タン酸の流出を防ぐものであれば何でもよいが、市販セ
ルロースエステルフィルターなどを好適に用いることが
できる。このシリンジ中に試料浴液を入れ、カラム中の
チタン酸を通して出口より浴出する処理液を容器に受は
捕集する。流出速度は任意であるが、小さいけど除去率
は高い□所安時間を考慮すれば!、 Oml/min程
度が効率的である。
The column can be made of any material as long as it does not denature the sample, but glass or stainless steel have sufficient strength. Inlets and outlets (6) and (7) with filters (3) are provided at both ends of this column, one of which serves as the inlet for the sample and supplies the sample bath liquid (co), for example, with a syringe (1), and the other serves as the inlet for the processing liquid. Exit ζ. The filter (3) may be of any type as long as it prevents the outflow of titanic acid, but commercially available cellulose ester filters and the like can be suitably used. A sample bath solution is put into this syringe, and the processing solution that passes through the titanic acid in the column and comes out from the outlet is collected in a container. The outflow speed is arbitrary, but although it is small, the removal rate is high □ If you take into account the safe time! , about Oml/min is efficient.

本発明は以上のごとく非常に簡単な方法で溶液中に含ま
れる極性有機化合物f、吸着除去できるものであり、ま
た吸着した極性有機化合物はアルカリ性溶液を溶離液と
して流すことにより回収することが出来る□ 次に実施例を用いて本発明の詳細な説明するが、本発明
はその要旨を越えない限り以下の実施例に限定されるも
のではない。
As described above, the present invention is capable of adsorbing and removing polar organic compounds f contained in a solution using a very simple method, and the adsorbed polar organic compounds can be recovered by flowing an alkaline solution as an eluent. □ Next, the present invention will be explained in detail using Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

て造粒成形されたチタン絵粒状物を粉砕機によたチタン
酸ユ09を図に示すようなカートリッジ内に充填し上下
を市販セルロース・エステルフィルターで封じた。この
カートリッジ上部の試料注入口にガラスシリンジを取り
付は蒸留水に俗解させた生肝フィブリ/−ゲンの水浴液
(fljIB t o o pg/rnl )よOml
を流速ユ!r mJ/m1llでチタン酸中を通液させ
た。処理液出口で口液を回収し、処理液中の生肝フィブ
リ/−ゲン濃度をTOC法によって定置するとよθμ9
/mノであった。部ち生肝フィブリノーゲンの除去率は
9j%である。同様にして、卵アルブミン、除去した結
果をまとめると次表の如くであった。
The titanium granules granulated using a pulverizer were filled with titanate 09 into a cartridge as shown in the figure, and the top and bottom were sealed with commercially available cellulose ester filters. Attach a glass syringe to the sample injection port on the top of this cartridge and add Oml of raw liver fibril/gen water bath solution (fljIB to pg/rnl) mixed with distilled water.
Flow velocity! The titanic acid solution was passed through at rmJ/ml. Collect the oral fluid at the treatment solution outlet, and determine the live liver fibril/gen concentration in the treatment solution using the TOC method.
/mノ. The removal rate of raw liver fibrinogen was 9j%. Similarly, ovalbumin was removed, and the results were summarized in the following table.

極性物5M−特にアミノ酸、タンパク寅、酵素類が効果
的に吸着除去されていることが知見される。
It is found that polar substances 5M - particularly amino acids, proteins, and enzymes - are effectively adsorbed and removed.

【図面の簡単な説明】[Brief explanation of drawings]

図面は本発明を実施するのに好適な装置の一例を示!も
のである。 l・°・ガラス・シリンジ コ・・・試料溶液3・・・
セルロー、スエステルフィルターダ・・・整粒チタン酸 S・・・ステンレススチールカートリッジ6・・・試料
注入口 ア・・・処理液田口
The drawings show an example of a device suitable for carrying out the invention! It is something. l・°・Glass syringe Co...sample solution 3...
Cellulose, Sester filter d...Sized titanate S...Stainless steel cartridge 6...Sample injection port a...Processing liquid Taguchi

Claims (1)

【特許請求の範囲】 (1)  電離基を有する極性有機化合物を含む溶液を
、二酸化チタン水和物に接触させ、該極性有機化合物を
吸着させることを特徴とする極性有機化合物の吸着除去
方法口 (コ)電離基を有する極性有機化合物がア之ノ酸類、蛋
白質、酵素類であることを特徴とする特許請求の範囲第
7項記載の吸着除去方法。 (3)二酸化チタン水和物の粒径がgo〜1000μで
あることを特徴とする特許請求の範囲97項又は第一項
記載の吸着除去方法。
[Scope of Claims] (1) A method for adsorption and removal of polar organic compounds, which comprises bringing a solution containing a polar organic compound having an ionizing group into contact with hydrated titanium dioxide to adsorb the polar organic compound. (c) The adsorption removal method according to claim 7, wherein the polar organic compound having an ionizable group is an anoic acid, a protein, or an enzyme. (3) The adsorption removal method according to claim 97 or claim 1, wherein the titanium dioxide hydrate has a particle size of go to 1000μ.
JP16773681A 1981-10-20 1981-10-20 Adsorptive removal of polar org. compound Pending JPS5870835A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP16773681A JPS5870835A (en) 1981-10-20 1981-10-20 Adsorptive removal of polar org. compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP16773681A JPS5870835A (en) 1981-10-20 1981-10-20 Adsorptive removal of polar org. compound

Publications (1)

Publication Number Publication Date
JPS5870835A true JPS5870835A (en) 1983-04-27

Family

ID=15855176

Family Applications (1)

Application Number Title Priority Date Filing Date
JP16773681A Pending JPS5870835A (en) 1981-10-20 1981-10-20 Adsorptive removal of polar org. compound

Country Status (1)

Country Link
JP (1) JPS5870835A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5392505A (en) * 1991-10-29 1995-02-28 Canon Kabushiki Kaisha Method for mounting an elastic annular member

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5392505A (en) * 1991-10-29 1995-02-28 Canon Kabushiki Kaisha Method for mounting an elastic annular member

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