Search

JP-2026075391-A - metal adsorption material

JP2026075391AJP 2026075391 AJP2026075391 AJP 2026075391AJP-2026075391-A

Abstract

[Problem] One objective is to provide a new technical means that exhibits excellent metal adsorption for a wide range of heavy metals. [Solution] A metal adsorption material for adsorption of at least one heavy metal element selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Sn, Pb, and Bi, wherein the metal adsorption material is a silica support modified with at least an amino group-containing group represented by formula (I) and/or an amino group-containing group represented by formula (II). [Selection Diagram] None

Inventors

  • 八木 魁人
  • 今仲 庸介
  • 上野 晋司

Assignees

  • エヌ・イーケムキャット株式会社

Dates

Publication Date
20260508
Application Date
20241022

Claims (16)

  1. A metal adsorption material for adsorption of at least one heavy metal element selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Sn, Pb, and Bi, The metal adsorption material is a silica support containing an amino group represented by formula (I): (In the formula, R1 is a divalent C1-20 hydrocarbon moiety which may be substituted with one or more substituents. Z1 is either a bond or NR2 , R2 is a hydrogen atom or a C1-20 hydrocarbon group which may be substituted with one or more substituents. R3 is a divalent C1-20 hydrocarbon moiety which may be substituted with one or more substituents. R4 is a hydrogen atom or a C1-20 hydrocarbon group which may be substituted with one or more substituents. and/or amino group-containing groups represented by formula (II): (In the formula, R5 is a divalent C1-20 hydrocarbon moiety which may be substituted with one or more substituents. Z2 is either a bond or NR6 . R 6 is a C1-20 hydrocarbon group which may be substituted with hydrogen or one or more substituents. R7 is a divalent C1-20 hydrocarbon moiety which may be substituted with one or more substituents. At least modified by, Metal adsorption material.
  2. The metal adsorption material according to claim 1, wherein the silica support is at least modified with an amino group-containing group represented by formula (I).
  3. The metal adsorption material according to claim 1, wherein the silica support is modified with at least an amino group-containing group represented by formula (I) and an amino group-containing group represented by formula (II).
  4. The metal adsorption material according to claim 1, wherein R1 is C1 to 20 alkylene.
  5. The metal adsorption material according to claim 1, wherein Z1 is NR2 .
  6. The metal adsorption material according to claim 1, wherein R3 is C1-20 alkylene.
  7. The metal adsorption material according to claim 1, wherein R4 is C1-20 alkyl.
  8. The metal adsorption material according to claim 1, wherein R5 is C1-20 alkylene.
  9. The metal adsorption material according to claim 1, wherein Z2 is NR6 .
  10. The metal adsorption material according to claim 1, wherein R7 is C1-20 alkylene.
  11. The metal adsorption material according to claim 3, wherein the molar ratio (amino group represented by formula (II) / amino group represented by formula (I)) of the amino group-containing group on the silica support is 0.1 to 10.
  12. The metal adsorption material according to claim 1, wherein the average particle size (D10) of the silica carrier is 10 to 300 μm.
  13. A metal adsorption material according to claim 1, for the manufacture of electronic equipment manufacturing solutions.
  14. A method for producing a metal adsorption material according to any one of claims 1 to 13, Compounds represented by formula (III): (wherein R1 , Z1 , R3 , and R4 are as defined in claim 1, and each R8 is independently a C1-20 hydrocarbon group which may be substituted with one or more substituents.) and/or compounds represented by formula (IV): (In the formula, R5 , Z2 , and R7 are as defined in claim 1, and each R9 is independently a C1-20 hydrocarbon group which may be substituted with one or more substituents.) A method comprising the step of bringing into contact with a silica support.
  15. The method according to claim 14, wherein the compound represented by formula (III) comprises at least one selected from the group consisting of 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropyldiethoxysilane.
  16. The method according to claim 14, wherein the compound represented by formula (IV) comprises at least one selected from the group consisting of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane.

Description

This disclosure relates to metal adsorption materials. In recent years, there has been an increasing demand for removing trace amounts of heavy metals from products used in pharmaceuticals, catalysts, electronic components, and semiconductor manufacturing. More specifically, photoresists and cleaning solutions used in semiconductor manufacturing, pharmaceuticals and their intermediates, synthesis catalysts, and fuel cell catalysts can suffer unexpected adverse effects such as reduced yield, side effects, decreased performance, and increased by-products if the final product contains heavy metals at ppm levels. In particular, heavy metal components exist not only as metal ions in solution but also as complexes and metal oxide colloidal particles, making complete removal difficult. Therefore, various technologies for removing heavy metal elements (e.g., metal adsorption materials) are being investigated. For example, Patent Document 1 discloses a technique for adsorbing heavy metals in trace amounts using a chelate resin having hydroxyl groups, amine groups, or thiol groups on a support of silica, a silica-containing substance, polystyrene, or crosslinked porous polystyrene. Patent Document 2 discloses a technique for removing metallic elements such as calcium, iron, and nickel by using a compound in which naphthaleneamine and a phenyl group are bonded together with activated carbon. Patent Document 3 discloses a technique for removing iron and nickel by using polyimide resin or polyamide-imide resin. International Publication No. 2019/131629International Publication No. 2020/241416International Publication No. 2016/125832 According to one embodiment of the present disclosure, a metal adsorption material for adsorbing at least one heavy metal element selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Sn, Pb, and Bi, The above metal adsorption material has a silica support containing an amino group represented by formula (I): (In the formula, R1 is a divalent C1-20 hydrocarbon moiety which may be substituted with one or more substituents. Z1 is either a bond or NR2 , R2 is a hydrogen atom or a C1-20 hydrocarbon group which may be substituted with one or more substituents. R3 is a divalent C1-20 hydrocarbon moiety which may be substituted with one or more substituents. R4 is a hydrogen atom or a C1-20 hydrocarbon group which may be substituted with one or more substituents. and/or amino group-containing groups represented by formula (II): (In the formula, R5 is a divalent C1-20 hydrocarbon moiety which may be substituted with one or more substituents. Z2 is either a bond or NR6 . R 6 is a C1-20 hydrocarbon group which may be substituted with hydrogen or one or more substituents. R7 is a divalent C1-20 hydrocarbon moiety which may be substituted with one or more substituents. At least modified by, A metal adsorption material is provided. The metal adsorption material of this disclosure will be described in detail below. [Silica Elevator] The "silica carrier" in this disclosure is not particularly limited, as long as it is capable of grafting an amino group-containing group represented by formula (I) and/or an amino group-containing group represented by formula (II). Compared to other types of carriers (e.g., alumina carriers, carbon-based carriers), silica carriers are advantageous in that they contain a large number of hydroxyl groups on their surface, making them more likely to form silicon-oxygen bonds (Si-O bonds) (i.e., easier to graft an amino group-containing group represented by formula (I) and/or an amino group-containing group represented by formula (II)). The silica carrier may be particulate, gel-like, or colloidal. From the viewpoint of ease of filtering out the metal adsorbent material in the reaction system, the silica carrier is preferably particulate. The silica platform may have a molded geometric shape, such as a sphere, cylinder, or cylindrical shape, or its space may be partitioned by walls of any shape. From the viewpoint of more efficiently adsorbing heavy metal elements and/or preventing clogging during filtration of metal adsorbent materials, a spherical silica platform is preferable. The size of the silica carrier is not particularly limited as long as it can achieve the objectives of this disclosure. A larger geometric surface area per unit volume or per unit weight in the bulk state of the silica carrier may allow for the grafting of more amino group-containing groups represented by formula (I) and/or formula (II). On the other hand, if the surface area of the silica carrier becomes too large, efficient filtration may not be possible. From this viewpoint, the silica carrier may, for example, have a volume-based cumulative 10% particle diameter (D10 diameter) of about 10 to about 300 μm, preferably about 20 to about 200 μm, more preferably about 30 to about 100 μm, and even more preferably about 40 to about 80 μm. Note that the D10 diameter in this disclosure is a v