JPH0422439A - Organic compound and method for purifying its solution - Google Patents

Abstract

PURPOSE:To absorb and remove a metal ion by bringing a metal ion-containing org. compound into contact with a chelate resin having an aminocarboxylic acid group and/or an iminocarboxylic acid group. CONSTITUTION:As a chelate resin, a resin having an aminocarboxylic acid group and/or an iminocarboxylic acid group obtained by reacting a polymer having an amine reactive group with amino acid compound is used. An org. compound containing a metal ion such as a Cu or Ag ion or a solution thereof is brought into contact with the chelate resin by passing the same through a tower packed with said chelate resin or by immersing the chelate resin in the org. compound or the solution thereof, and subsequently separating the same by filtering. The chelate resin having the metal ion adsorbed thereon is regenerated to be capable of being repeatedly used. By this method, the metal ion is efficiently removed.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for purifying an organic compound containing metal ions or a solution thereof. More specifically, the present invention relates to a method for efficiently removing metal ions as impurities in an organic compound or a solution thereof using a specific chelate resin.

<Prior Art> Organic compound products manufactured and used in chemical, pharmaceutical, and food factories contain metal ions, which are impurity elements, to a greater or lesser extent. For example, taking mercury,
Sake is 0,005ppm, beer is 02 sips 04-0
．． 006ppm, lactic acid drinks 0.018-0. O3
lppm C Polymer Processing, Volume 23, Page 377 (197
4) Contains. Metal ions in such products originate from metal ions existing in living organisms as raw materials, entrainment during the manufacturing process, elution from manufacturing equipment materials, contamination from the manufacturing environment, etc. Regulations on metal ions in such organic compound products are becoming increasingly strict as analytical technology improves.

In general, filtration and adsorption treatment using activated carbon and ion exchange resins are known as methods for removing trace impurities in liquids. In particular, adsorption treatment using ion exchange resins is widely used to remove ionic components from aqueous solutions. There is.

<Problems to be Solved by the Invention> However, treatment with a normal ion exchange resin is not necessarily satisfactory in terms of the degree of removal of metal ions. In particular, with respect to organic compound products having carboxyl groups in their molecules, satisfactory results cannot be obtained because the carboxyl groups and metal ions in the products form ionic or chelate bonds.

111. In view of these circumstances, the present inventors conducted intensive studies to find a method for efficiently removing metal ions from organic compounds, particularly organic compounds having carboxyl groups, or solutions thereof, and found that aminocarboxylic acid groups and/or iminocarboxylic acids The present inventors have discovered that chelate resins having a group have good selective adsorption properties for metal ions in organic compounds and have a large adsorption capacity, leading to the completion of the present invention.

Means for Solving the Problems> The present invention involves contacting an organic compound containing a metal ion or a solution thereof with a chelate resin having an aminecarboxylic acid group and/or an iminocarboxylic acid group to remove the metal contained in the organic compound. This is a method for purifying an organic compound or a solution thereof, which is characterized by adsorbing and removing ions.

The chelate resin used in the present invention is a chelate resin having an aminocarboxylic acid group and/or an iminocarboxylic acid group, and the resin base, shape, and manufacturing method are not particularly limited. Generally, the following are exemplified.

(1) Chloromethyl group, sulfonyl chloride group, carbonyl chloride group, 2) IJ group, m-4=Ki) Isocyanate group, epoxy group, aldehyde group, halogen atoms of chlorine, bromine, iodine, etc. A resin obtained by reacting a polymer having an amine-reactive group with an amino acid compound such as glycine, alanine, β-alanine, iminodiacetic acid, iminodipropionic acid, ethylenediaminetriacetic acid, or ethylenediaminetriacetic acid, (2) An amino resin having a primary or secondary amino group is added with a halogenated alkylcarboxylic acid compound such as monochloroacetic acid, monobromoacetic acid, monochloropropionic acid,
A resin obtained by reacting monobromopropionic acid or a salt of an alkali metal or alkaline earth metal thereof, (3) an amino resin having a primary or secondary amino group, and acrylic acid, methacrylic acid, or acetylene dicarboxylic acid. acids, maleic acid, or alkali metals of these acids,
Examples include resins obtained by reacting alkaline earth metal salts, methyl, ethyl esters, etc. (hereinafter referred to as acrylic acid compounds), and further hydrolyzing the esters. These resins are Sumikylate MC-
30, MC-75, MC-76 (J21flt Yukagaku 2
fv), Duolite C-466 (manufactured by Duolite International), Diaion CR-10 (manufactured by Mitsubishi Kasei), Unicelec [IR-10, 20, 30, 4
It is commercially available as 0, 50, (manufactured by Unitika), etc.

The organic compound or its solution that is the subject of the present invention contains metal ions as impurities, and forms a strong chelate bond with the aminocarboxylic acid group and/or iminocarboxylic acid group of the chelate resin that is equivalent to or stronger than that of the metal ion. There are no particular limitations on the solution as long as it is a solution of an organic compound that does not require any chemical reaction.

Further, when these organic compounds themselves are liquid at room temperature, the organic compounds themselves may be used.

Examples include methyl alcohol, ethyl alcohol, propyl alcohol, methyl alcohol, subvaragic acid,
Asparagine, arginine, nstine, glutamic acid, glutamine, glutamine, histidine, inroinone,
Amino acids such as loin, lysine, methionine, ornithine, phenylalanine, proline, serine, threonine, tryptophan, thyronine, valine, alkali metal salts or mineral salts of these 7 amino acids, glucose, fructose, amylose, glycogen, lectin, galactose , cellulose, glucomannan, galactomannan, cyclodextrin, fructan, sugars such as oligosaccharides, adenine, guanine, cytonin, uracil,
Thymine, adenosine, inosine, guanosine, thymidine, 5'-adenylic acid, 5'-inosinic acid, 5'-guanylic acid, 5'-xanicylic acid, 5'-cytidylic acid, 5'-
Nucleic acid compounds such as uridylic acid and 5'-thymidylic acid, thiamine, thiamine monophosphate, hydroxyethylthiamine riboflavin, furapin 5'-phosphate, pyridoxine, pyridoxal, pyridoxamine, pyridoxine 5-phosphate, nicotinic acid, nicotinamide , pantothenic acid, folic acid, ribic acid, vitamins such as biotin, adipic acid, aniline, phenol, morpholine, coumarin, uric acid, anthraquinone, pyridine, naphthol, H acid, urothrobin, indophenol, rosolic acid, pyrogallol, J
Acids, pharmaceutical dye intermediates with groups such as quinoline, =0, -COOH, NL>0 or >till, >C=0, -, such as urea, thiourea, melamine, dimethylformamide, dimethylsulfoxide, etc. Organic chemicals containing NH or > C=S groups, soy sauce, sake, shochu, lactic acid,
Acidic, neutral, organic compounds such as fermented liquids such as amino acids and nucleic acids, and fruit juices of fruits such as oranges, tangerines, apples, and grapes.
Examples include alkaline aqueous solutions and organic compounds themselves when they are liquid at room temperature.

In particular, in the case of organic compounds having carboxyl groups in their molecules, it is extremely difficult to remove impurity ions using ion exchange resins since they are difficult to form stable complexes with metal ions. Treatment with a chelate resin having a carboxylic acid group is particularly effective.

There is no particular restriction on the bonding force as long as it is stronger than the bonding force between the organic compound soluble metal ion and the organic compound solution, which are the objects of purification in the present invention.

To illustrate, Cu of group IB of the periodic table, Δg1Δu, Mg, Ca, Sr, Ba, Zn, Cd, Hg, I[I
Δ1SGa, In, Tl5Sc of the family.

￥1■ Group of Fe, Co, Ni, Ru, Rh, Pa, 0s
Spt, rank-made elements La, Ce.

Examples include ions of Pr1Nd, Pm, Sm, Fu, Cd, Lu, and actinide element U.

The chelate resin having an aminocarboxylic acid group and/or an iminocarboxylic acid group used in the present invention has high adsorption properties for metal ions, especially metal ions of divalent or higher valence, and has a high adsorption property for metal ions that form chelates with organic compounds. Since it also has adsorption properties for ions, it is preferably used for removing metal ions contained in such organic compounds. When the solution of the organic compound to be brought into contact with the chelate resin is an aqueous solution of the organic compound, it is generally carried out at a pH in the range of 2 to 10, but depending on the type of metal ion, it is possible to carry out in the entire pH range, and the conditions are as follows: It can be set by conducting appropriate preliminary experiments.

The method of contacting the organic compound or its solution with the chelate resin is not particularly limited, and may include a method of passing the organic compound or its solution into a tower filled with the chelate resin, a method of passing the chelate resin into the organic compound or its solution, Examples include a method of soaking and then filtering and separating. The contact temperature between the organic compound or its solution and the chelate resin is not particularly limited either (usually it can be carried out at 0 to 110°C, but it is possible to cut the bond between the organic compound and the metal ion and the contact between the metal ion and the chelate resin). In order to accelerate the bonding, a high temperature is desirable, preferably 40 to 100°C, particularly preferably 50 to 100°C.The contact time is also not particularly limited.

The amount of chelate resin to be used, the contact temperature, the contact time, etc. relative to the amount of the organic compound or its solution can be determined by appropriately conducting preliminary experiments.

The impurity metal ions adsorbed by the chelate resin of the present invention can be eluted and recovered using a suitable eluent. As the eluent, an acidic aqueous solution such as hydrochloric acid or nitric acid having a concentration of 1 to 6 normal is generally used, although it varies depending on the type of adsorbed metal ion.

After desorbing impurity metal ions in this way, the chelate resin can be used as is, or if necessary, oxidized with water and/or hydroxide. After treatment with an aqueous mineral acid solution such as nitric acid, it can be repeatedly used to adsorb organic compounds or metal ions that are impurities in the solution.

<Effects of the Invention> The chelate resin having an aminocarboxylic acid group and/or an iminocarboxylic acid group of the present invention has good selective adsorption properties for metal ions that are impurities in organic compounds or solutions thereof, and has a large adsorption capacity for metal ions. It is effective for purifying organic compounds containing metal ions or solutions thereof because they can significantly lower the adsorption equilibrium concentration of metal ions, and their industrial value is extremely large.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the Examples.

Example 1 A commercially available chelate resin having an aminocarboxylic acid group, Sumikire IC-75 (manufactured by Sumima Kagaku Kogyo Co., Ltd.) (hereinafter, this resin will be referred to as chelate resin A).

) 3.2mg/j of iron in a column packed with 20ml!
An organic acid aqueous solution (acetic acid 12%, glutaric acid 8%,
Contains 4% adipic acid) 20β in a downward flow, 5V10H
When the liquid was passed at room temperature at a rate of r', the metal concentration in the effluent was 0.01 mg/j! It was below.

Examples 2 and 3 The chelate resin A having an aminocarboxylic acid group used in Example 1 was replaced with Sumikylate'MC-30 (manufactured by Sumima Kagaku Kogyo Co., Ltd., a commercially available chelate resin having an iminodiacetic acid group).
(Hereinafter, this resin will be referred to as chelate resin B) UNICEREC "V" is a commercially available chelate resin having 1 iminodiacetic acid group.
R-30 (manufactured by Unitika Co., Ltd., hereinafter referred to as chelate resin C)
An adsorption test was conducted in the same manner as in Example 1, except that the material was changed to (referred to as ). The results are shown in Table 1.

Table 1 Comparative Examples Except for changing the chelate resin having an aminocarboxylic acid group used in Example 1 to a commercially available weakly acidic ion exchange resin "DENORAI" C-464 (manufactured by Rohm and Haas) An adsorption test was conducted in the same manner as in Example 1.

The results are shown in Table 2.

Table 2 (Margin below)

Claims (2)

[Claims] (1) The organic compound containing a metal ion or its solution is brought into contact with a chelate resin having an aminocarboxylic acid group and/or an iminocarboxylic acid group to adsorb and remove the metal ion in the organic compound. A method for purifying organic compounds or their solutions. (2) The method for purifying an organic compound or a solution thereof according to claim 1, wherein the organic compound has a carboxyl group in its molecule.