JP6300205B2 - High-purity siliceous material using copper smelting slag as raw material and method for producing the same - Google Patents
High-purity siliceous material using copper smelting slag as raw material and method for producing the same Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 62
- 229910052802 copper Inorganic materials 0.000 title claims description 62
- 239000010949 copper Substances 0.000 title claims description 62
- 239000000463 material Substances 0.000 title claims description 53
- 238000003723 Smelting Methods 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000002994 raw material Substances 0.000 title description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 90
- 239000000499 gel Substances 0.000 claims description 71
- 238000000034 method Methods 0.000 claims description 38
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 21
- 239000000017 hydrogel Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 17
- 238000002386 leaching Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000003463 adsorbent Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 230000004907 flux Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000010306 acid treatment Methods 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000009628 steelmaking Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明は、銅製錬スラグを原料とする高純度ケイ酸質材料及びその製造方法に関する。 The present invention relates to a high-purity siliceous material using copper smelting slag as a raw material and a method for producing the same.
スラグは金属製錬の過程で発生する副産物である。スラグには、鉄を製錬する過程で生じる製鋼スラグや製鉄スラグ、銅を製錬する過程で生じる銅製錬スラグ等がある。 Slag is a by-product generated during the metal smelting process. Examples of the slag include steelmaking slag and ironmaking slag generated in the process of smelting iron, and copper smelting slag generated in the process of smelting copper.
製鋼スラグや製鉄スラグは、コンクリート原料やゼオライトの原料として再利用が進んでいる。特許文献１には鉄を生産する際に生じる高炉スラグを酸処理し、シリカゲルを分離した後、ゼオライトを製造する方法が記載されている。 Steelmaking slag and steelmaking slag are being reused as raw materials for concrete and zeolite. Patent Document 1 describes a method of producing zeolite after acid-treating blast furnace slag generated when iron is produced and separating silica gel.
また、特許文献２には、高炉スラグを混合した造粒処理材を地盤材料として用いることが開示されている。 Patent Document 2 discloses using a granulated material mixed with blast furnace slag as a ground material.
一方、銅鉱石から粗銅を取り出す銅製錬工程において生じる銅スラグは、製鋼スラグや製鉄スラグと比較すると、鉄の含有量が多く、また密度が大きいため、サンドブラスターの研削材や高比重コンクリートの原料など、限定的な用途しかない（非特許文献１、２）。 On the other hand, copper slag generated in the copper smelting process for extracting crude copper from copper ore has a higher iron content and higher density than steelmaking slag and ironmaking slag, so it is a raw material for sandblaster abrasives and high-density concrete. There are only limited uses (Non-Patent Documents 1 and 2).
銅スラグをコンクリートに混ぜ込むと重く丈夫なものができるという利点もあるが、それ以上に、フレッシュコンクリート等において、固体材料の沈降又は分離によって、混練水の一部が遊離して上昇するブリーディングの作用が大きくマイナスに働くことが知られている。ブリーディングが生じるとコンクリート内部に水みちを形成し、密実性を損なうため、コンクリートの強度が低下する。 In addition to the advantage that copper slag is mixed with concrete, it can be made heavy and strong. However, in fresh concrete etc., bleeding of some of the kneading water rises due to sedimentation or separation of solid materials. It is known that the effect is greatly negative. When bleeding occurs, a water channel is formed inside the concrete and the solidity is impaired, so that the strength of the concrete decreases.
そのため、全国で年間およそ２５０万トンの銅製錬スラグが排出されているにも関わらず、大部分は堆積保管されているのが現状である。 Therefore, despite the fact that approximately 2.5 million tons of copper smelting slag is discharged nationwide, most of it is currently stored in storage.
銅製錬スラグは、再利用方法が限られているため、その大部分を堆積保管するか、産業廃棄物として処理するしかなく、有効で付加価値の高い再利用方法が検討されていた。 Since copper smelting slag is limited in its reuse method, most of it has to be deposited and stored or treated as industrial waste, and an effective and high added value reuse method has been studied.
本発明は、鉄含量が多いことを活かした吸着材を銅製錬スラグから製造する方法を提供することを課題とする。 This invention makes it a subject to provide the method of manufacturing the adsorbent which utilized the high iron content from copper smelting slag.
また、該方法により製造されたゲルの吸着材としての利用、及び銅製錬プロセスへ該ゲルを組み込むことにより再利用することを課題とする。 Another object is to use the gel produced by the method as an adsorbent and to reuse the gel by incorporating it into a copper smelting process.
本発明の銅製錬スラグから製造する高純度にケイ酸を含むケイ酸質材料の製造方法は、銅スラグを塩酸又は硝酸を含む水溶液で処理することによって、ヒドロゲルを生成し、前記ヒドロゲルを乾燥することを特徴とする。 In the method for producing a siliceous material containing silicic acid with high purity produced from the copper smelting slag of the present invention, a hydrogel is produced by treating copper slag with an aqueous solution containing hydrochloric acid or nitric acid, and the hydrogel is dried. It is characterized by that.
ここで、本発明で高純度にケイ酸を含むとは、最終生成物であるケイ酸質材料の７０％以上がケイ酸である生成物をいう。本発明でいうケイ酸質材料では、ケイ素以外の構成元素も金属酸化物として存在するために、酸素の含量が非常に多く６２％以上の重量を占めている。したがって、構成成分から酸素を除くと元素組成のうち、９０％以上がケイ素となる。 Here, high-purity silicic acid in the present invention means a product in which 70% or more of the siliceous material as the final product is silicic acid. In the siliceous material referred to in the present invention, constituent elements other than silicon are also present as metal oxides, so that the oxygen content is very large and occupies a weight of 62% or more. Therefore, when oxygen is excluded from the constituent components, 90% or more of the elemental composition is silicon.
製鋼スラグや製鉄スラグの再利用方法は、特許文献１に記載されているように、酸処理を行い生成したシリカゲルを分離し、その後、ゼオライトを製造することによる。 The method of reusing steelmaking slag and ironmaking slag is, as described in Patent Document 1, by separating the silica gel produced by acid treatment and then producing zeolite.
これに対し、本発明のケイ酸質材料の製造方法は、銅スラグを塩酸、又は硝酸で処理して得られたヒドロゲルをそのまま乾燥させることにより吸湿、吸着能を備えた乾燥ゲルを製造するものである。塩酸、又は硝酸で処理することにより、溶出したケイ酸成分が互いに結びつくため、水と鉄イオンを多く含んだケイ酸ヒドロゲルが生成され、したがって、少ない工程で非常に簡便に銅製錬スラグの再利用を図ることができる。 In contrast, the method for producing a siliceous material according to the present invention produces a dried gel having moisture absorption and adsorption capacity by directly drying a hydrogel obtained by treating copper slag with hydrochloric acid or nitric acid. It is. By treating with hydrochloric acid or nitric acid, the eluted silicic acid components are combined with each other, resulting in the production of a silicic acid hydrogel rich in water and iron ions. Can be achieved.
製鋼スラグや製鉄スラグでは酸浸出を行うことが既に報告されているが、本発明者らは、銅製錬スラグを酸処理する際にどのような酸でも使用可能なわけではないことを明らかにした。銅製錬スラグでは、塩酸、又は硝酸を用いた場合に、ヒドロゲルが生成し、有効な再利用ができることを明らかにした。 Although it has already been reported that acid leaching is performed in steelmaking slag and ironmaking slag, the present inventors have clarified that not any acid can be used when acidizing copper smelting slag. . In copper smelting slag, when hydrochloric acid or nitric acid was used, hydrogel was formed, and it was clarified that it could be reused effectively.
また、本発明は前記ケイ酸質材料の製造方法において、前記ヒドロゲルを乾燥することにより得られた前記ケイ酸質材料を焼成することによってゲルを得ることを特徴とする。 In the method for producing a siliceous material, the present invention is characterized in that a gel is obtained by firing the siliceous material obtained by drying the hydrogel.
ヒドロゲルを乾燥させた後に焼成すると、ゲル表面に主として鉄からなる金属皮膜が形成されるため、電気伝導性が付与されたゲルを製造することができる。電気伝導性を備えた焼成ゲルは軽量であり、電池材料や電極材料，ＬＣＤなどの導通材や異方性導電部材，帯電防止材，導電性塗料など、新たな用途を開拓することができる。 When the hydrogel is dried and then baked, a metal film mainly composed of iron is formed on the gel surface, so that a gel with electrical conductivity can be produced. The fired gel with electrical conductivity is lightweight, and can open up new applications such as battery materials, electrode materials, conductive materials such as LCD, anisotropic conductive members, antistatic materials, and conductive paints.
さらに、本発明は前記ケイ酸質材料の製造方法において、前記ヒドロゲルを乾燥することにより得られた前記ケイ酸質材料を酸浸出することによって吸着材を得ることを特徴とする。 Furthermore, the present invention is characterized in that in the method for producing a siliceous material, an adsorbent is obtained by acid leaching the siliceous material obtained by drying the hydrogel.
ヒドロゲルを乾燥させたケイ酸質材料を酸で浸出すると、鉄を中心とした金属成分が溶出し、ゲル個体内部にメソ孔が生成し、高い比表面積を有するケイ酸質材料となることが明らかとなった。通常のシリカゲルに比べて比表面積が高いことから、高い吸着能力が期待される。 It is clear that when a siliceous material dried from hydrogel is leached with acid, metal components centering on iron are eluted, and mesopores are generated inside the gel body, resulting in a siliceous material having a high specific surface area. It became. Since the specific surface area is higher than that of ordinary silica gel, a high adsorption capacity is expected.
さらに、本発明は前記ケイ酸質材料の製造方法において、前記ヒドロゲルを乾燥することにより得られた前記ケイ酸質材料を塩酸浸出することによって、前記吸着材の副生成物として凝集剤を得ることを特徴とする。 Furthermore, the present invention provides a flocculant as a by-product of the adsorbent by leaching the siliceous material obtained by drying the hydrogel in the method for producing the siliceous material. It is characterized by.
ヒドロゲルを乾燥させたケイ酸質材料は、鉄を中心とした金属成分を含むので、塩酸で浸出すると、塩化鉄を主成分とする金属の塩化物が得られる。塩化鉄は廃水中の微粒子の凝集剤として用いることが知られており、前記塩化物は凝集剤として使用することが期待される。 Since the siliceous material obtained by drying the hydrogel contains a metal component centered on iron, when leached with hydrochloric acid, a metal chloride containing iron chloride as a main component is obtained. It is known that iron chloride is used as a flocculant for fine particles in waste water, and the chloride is expected to be used as a flocculant.
さらに、本発明の銅製錬スラグから製造する高純度にケイ酸を含むケイ酸質材料を使用する方法は、前記いずれかのケイ酸質材料を銅製錬工程の融剤として再利用することを特徴とする。 Furthermore, the method of using a siliceous material containing silicic acid with high purity produced from the copper smelting slag of the present invention is characterized by reusing any one of the siliceous materials as a flux in a copper smelting process. And
銅製錬工程では、ケイ酸を融剤として用いている。本発明のケイ酸質材料はケイ酸を高
純度で含むことから、銅製錬工程で再利用することが可能である。銅スラグから生じたケイ酸質材料をそのまま再利用することは、銅製錬のコスト低減にもつながることから、非常に有用な利用方法である。
In the copper smelting process, silicic acid is used as a flux. Since the siliceous material of the present invention contains silicic acid at a high purity, it can be reused in the copper smelting process. Reusing the siliceous material generated from copper slag as it is leads to cost reduction of copper smelting, and is a very useful utilization method.
本発明の銅製錬スラグより製造する高純度にケイ酸を含むケイ酸質材料は、銅製錬スラグを塩酸又は硝酸を含む水溶液で処理し、乾燥することによって製造することを特徴とする。 The high-purity siliceous material containing silicic acid produced from the copper smelting slag of the present invention is produced by treating copper smelting slag with an aqueous solution containing hydrochloric acid or nitric acid and drying it.
硝酸、又は塩酸で処理することにより、溶出したケイ酸成分が互いに結びつくため、水と鉄イオンを多く含んだケイ酸ヒドロゲルが生成され、これをそのまま乾燥させることにより吸湿、吸着能を備えた乾燥ゲルを得ることができる。 By treating with nitric acid or hydrochloric acid, the eluted silicic acid components are combined with each other, so a silicic acid hydrogel containing a large amount of water and iron ions is produced. By drying this, it is dried with moisture absorption and adsorption capacity. A gel can be obtained.
本発明のケイ酸質材料は、乾燥ゲルを焼成することを特徴とする。 The siliceous material of the present invention is characterized by firing a dried gel.
前記ケイ酸質材料を乾燥させた後に焼成すると、ゲル表面に主として鉄からなる金属皮膜が形成されるため、電気伝導性が付与されたゲルを得ることができる。軽量であり、さらに電気伝導性が付与されることにより、吸着材以外にも様々な用途が考えられる。 When the siliceous material is dried and then fired, a metal film mainly composed of iron is formed on the gel surface, so that a gel with electrical conductivity can be obtained. Since it is lightweight and further imparted with electrical conductivity, various uses other than the adsorbent can be considered.
本発明のケイ酸質材料は、乾燥ゲルを酸浸出することを特徴とする。 The siliceous material of the present invention is characterized by acid leaching of the dried gel.
ヒドロゲルを乾燥させた乾燥ゲルを酸で浸出すると、鉄を中心とした金属成分が溶出し、ゲル個体内部にメソ孔が生成し、高い比表面積を有する吸着材が得られる。通常のシリカゲルに比べて比表面積が高く、高い吸着能力を備えている。 When the dried gel obtained by drying the hydrogel is leached with an acid, metal components centering on iron are eluted, and mesopores are generated inside the gel solid, thereby obtaining an adsorbent having a high specific surface area. Compared with normal silica gel, it has a high specific surface area and high adsorption capacity.
本発明のケイ酸質材料の副生成物としての凝集剤は、乾燥ゲルを塩酸浸出することを特徴とする。 The flocculant as a by-product of the siliceous material of the present invention is characterized by leaching the dried gel with hydrochloric acid.
ヒドロゲルを乾燥させた乾燥ゲルを塩酸で浸出すると、塩化鉄を主成分とする金属の塩化物が得られ、該塩化物は凝集剤として使用することが期待される。 When a dried gel obtained by drying a hydrogel is leached with hydrochloric acid, a metal chloride containing iron chloride as a main component is obtained, and the chloride is expected to be used as a flocculant.
一般に銅スラグは、鉄を多く含み、酸化鉄（ＦｅＯ）が４５〜５５％、二酸化ケイ素（ＳｉＯ2）が３０〜３６％程度含まれ、酸化カルシウム（ＣａＯ）が２〜７％、酸化アルミニウム（Ａｌ２Ｏ３）が３〜６％程度含まれている（非特許文献３）。 Generally copper slag, rich in iron, iron oxide (FeO) 45 to 55% of silicon dioxide (SiO 2) is contained about 30 to 36%, calcium oxide (CaO) 2 to 7% of aluminum oxide ( Al 2 O 3 ) is contained in an amount of about 3 to 6% (Non-patent Document 3).
銅製錬スラグは、鉄を多く含む点で鉄鋼スラグとは大きく異なるものの、二酸化ケイ素、酸化カルシウムを多く含む点では、鉄鋼スラグと同様の化学組成となっている。そこで、銅製錬スラグも、鉄鋼スラグと同様にシリカゲルの製造や金属抽出に利用できないか検討を行った。 Although copper smelting slag differs greatly from steel slag in that it contains a lot of iron, it has the same chemical composition as steel slag in that it contains a lot of silicon dioxide and calcium oxide. Therefore, we examined whether copper smelting slag could be used for silica gel production and metal extraction as well as steel slag.
鉄やケイ素はｐＨ１．０以下の低いｐＨ条件で溶出することが知られている。そこで、硫酸、硝酸、塩酸、及び比較のために水酸化ナトリウムを用いて浸出試験を行った。 It is known that iron and silicon are eluted under a low pH condition of pH 1.0 or less. Therefore, a leaching test was conducted using sulfuric acid, nitric acid, hydrochloric acid, and sodium hydroxide for comparison.
まず、スラグをエネルギー分散型Ｘ線分析装置（ＥＤＸ）で分析し、元素の定量を行った。元素組成は表１のとおりであった。その後、スラグ２．０ｇを各溶液５０ｍｌに浸漬し、２４時間振とうし、濾別した処理後のスラグを再度ＥＤＸにより分析を行い、元素の構成比率の変化を解析した。また、各試料について、走査型電子顕微鏡（ＳＥＭ）とＸ線分析装置（ＸＲＤ）により解析した。 First, slag was analyzed with an energy dispersive X-ray analyzer (EDX), and the elements were quantified. The elemental composition was as shown in Table 1. Thereafter, 2.0 g of slag was immersed in 50 ml of each solution, shaken for 24 hours, and the filtered slag was analyzed again by EDX to analyze changes in the constituent ratio of the elements. Each sample was analyzed by a scanning electron microscope (SEM) and an X-ray analyzer (XRD).
６Ｍ、３Ｍ、１Ｍ 水酸化ナトリウム水溶液で処理を行ったが、各濃度で大きな差は見られなかった。６Ｍ 水酸化ナトリウム処理前後での組成を表２に、外観の変化を図１に示す。表２は、処理後の構成元素の比率（ｗｔ％）、それぞれの重量（ｗｔ）、処理前スラグからの重量変化（Δｗｔ）、抽出率を示す。なお、抽出率が負の値であるということは、処理後の方がその元素の比率が増大したことを示している。また、処理前スラグの重さは２．０１２ｇ、処理後のスラグの重さは１．９３９ｇであり、重量は３．６％減少したのみである。 Treatment with 6M, 3M, 1M aqueous sodium hydroxide was performed, but no significant difference was observed between the concentrations. The composition before and after the 6M sodium hydroxide treatment is shown in Table 2, and the change in appearance is shown in FIG. Table 2 shows the ratio (wt%) of the constituent elements after treatment, the respective weights (wt), the weight change from the slag before treatment (Δwt), and the extraction rate. In addition, that the extraction rate is a negative value indicates that the ratio of the element increased after the treatment. Moreover, the weight of the slag before a process was 2.012g, the weight of the slag after a process was 1.939g, and the weight reduced only 3.6%.
水酸化ナトリウム処理によっては、カルシウムが若干抽出されただけで、濃度によらず外見・組成ともに大きい変化は見られなかった。図１（Ａ）に処理前のＳＥＭ画像を、図１（Ｂ）に水酸化ナトリウム処理後のＳＥＭ画像を示す。 By sodium hydroxide treatment, calcium was extracted only slightly, and no significant changes in appearance and composition were observed regardless of the concentration. FIG. 1A shows an SEM image before treatment, and FIG. 1B shows an SEM image after sodium hydroxide treatment.
一方、酸処理した場合には、ほとんどの金属成分が抽出され、スラグは手でつぶせるほど軟らかくなっていた。６Ｍ 硫酸で処理した場合の処理後のスラグ組成を表３に示す。なお、処理前スラグの重さは１．９９ｇ、処理後スラグの重さは１．２２ｇであり、重量は３８．７％減少していた。アルカリ抽出に比べ、１０倍程度の重量減少が生じており、銅スラグから多くの金属成分が抽出されていることを示す。 On the other hand, in the case of acid treatment, most of the metal components were extracted, and the slag was so soft that it could be crushed by hand. Table 3 shows the slag composition after the treatment with 6M sulfuric acid. In addition, the weight of the slag before a process was 1.99g, the weight of the slag after a process was 1.22g, and the weight was reducing 38.7%. Compared to alkali extraction, a weight reduction of about 10 times occurs, indicating that many metal components are extracted from copper slag.
なお、ここではデータを示していないが、ｐＨ１．０以下、すなわち約０．１Ｍの酸であれば、いずれの酸を用いても酸浸出を行うことが可能であった。 Although data is not shown here, acid leaching can be performed using any acid as long as the acid has a pH of 1.0 or less, that is, about 0.1 M acid.
酸処理を行うことにより、鉄、亜鉛は顕著に抽出され、いずれも９０％以上、抽出できることが明らかとなった。また、上記で述べたように水酸化ナトリウムによる浸出に比べ、重量が顕著に減少していることも、酸を用いた場合に多くの金属が抽出されていることを示している。 It was revealed that iron and zinc can be remarkably extracted by acid treatment, and both can be extracted by 90% or more. In addition, as described above, the weight is significantly reduced as compared with leaching with sodium hydroxide, which indicates that a lot of metal is extracted when using acid.
上記で示すように、酸浸出によって銅スラグから多くの金属が抽出されることから、これら金属成分を分離し再利用することは技術的には可能である。しかしながら、銅スラグに含まれている金属成分が多様であり、単一の金属として精製することは、実用面、コスト面から現実的ではないと考えられる。そこで、酸浸出後のスラグをヒドロゲルとして再利用する可能性を検討した。 As indicated above, since many metals are extracted from copper slag by acid leaching, it is technically possible to separate and reuse these metal components. However, there are various metal components contained in copper slag, and it is considered impractical to purify as a single metal from the practical and cost viewpoints. Therefore, the possibility of reusing slag after acid leaching as a hydrogel was investigated.
硫酸、硝酸、塩酸いずれの酸で処理した場合も、銅スラグから金属成分が抽出される点は同じだが、塩酸、硝酸で浸出を行うと、浸出後のスラグの形状には大きな差があることがわかった。図１（Ｃ）には硫酸処理後の乾燥ゲルのＳＥＭ画像を、図１（Ｄ）には塩酸処理後の乾燥ゲルのＳＥＭ画像を、図２（Ａ）には処理前の銅スラグ、図２（Ｂ）には硫酸処理後、図２（Ｃ）には塩酸処理後、図２（Ｄ）には硝酸処理後のゲルの写真を示す。 When treated with sulfuric acid, nitric acid, or hydrochloric acid, metal components are extracted from copper slag, but leaching with hydrochloric acid or nitric acid has a large difference in the shape of the slag after leaching. I understood. FIG. 1 (C) shows an SEM image of the dried gel after the sulfuric acid treatment, FIG. 1 (D) shows an SEM image of the dried gel after the hydrochloric acid treatment, FIG. 2 (A) shows a copper slag before the treatment, FIG. 2 (B) shows a photograph of the gel after the sulfuric acid treatment, FIG. 2 (C) after the hydrochloric acid treatment, and FIG. 2 (D) a gel after the nitric acid treatment.
図２に示すように、塩酸で処理すると、硫酸処理の場合と異なり、浸出液中にゲルが生成し、膨潤状態では添加したスラグの４〜５倍の質量となる。スラグ中の二酸化ケイ素が酸により溶出し、ゲル化したものと考えられる。なお、硝酸処理によっても塩酸処理と同様の結果が得られている。 As shown in FIG. 2, when treated with hydrochloric acid, unlike in the case of sulfuric acid treatment, a gel is formed in the leachate, and in the swollen state, the mass is 4 to 5 times that of the added slag. It is considered that silicon dioxide in the slag was eluted and gelled with acid. In addition, the result similar to hydrochloric acid treatment is obtained also by nitric acid treatment.
また、図１に示したＳＥＭ画像においても、処理前、あるいは水酸化ナトリウム処理に比べ、酸処理した場合には、スラグが小さくなっていることが確認された。特に硫酸処理後の銅スラグ（図１（Ｃ））は、脆弱になっていることもあり、処理前の銅スラグ（図１（Ａ））に比べ、大きさはかなり小さくなっている。 Moreover, also in the SEM image shown in FIG. 1, it was confirmed that the slag is small when the acid treatment is performed before the treatment or compared with the sodium hydroxide treatment. In particular, the copper slag after the sulfuric acid treatment (FIG. 1C) may be fragile, and the size is considerably smaller than the copper slag before the treatment (FIG. 1A).
元素組成等の解析を行うために、塩酸処理後のゲルを８０℃で２４時間乾燥し、ＥＤＸ及びＸ線回折により解析を行った。ＥＤＸスペクトルを図３（Ａ）に、Ｘ線回折パターンを図３（Ｂ）に示す。 In order to analyze the elemental composition and the like, the gel after the hydrochloric acid treatment was dried at 80 ° C. for 24 hours and analyzed by EDX and X-ray diffraction. An EDX spectrum is shown in FIG. 3 (A), and an X-ray diffraction pattern is shown in FIG. 3 (B).
図３（Ａ）に示すように、ゲルの組成は酸素、及びケイ素に富んだ組成となっており、スラグ中の二酸化ケイ素が酸により溶出し、ゲル化したものと考えられる。また、図３（Ｂ）に示すＸ線回折パターンにブロードなピークが２２°付近に現れていることから、非晶質のシリカが存在することが確認された。また、ピークの位置より、その内部にはクリストバライトの結晶構造を有している部分が存在しているものと考えられる。 As shown in FIG. 3A, the composition of the gel is rich in oxygen and silicon, and it is considered that the silicon dioxide in the slag was eluted by the acid and gelled. In addition, since a broad peak appears in the X-ray diffraction pattern shown in FIG. 3B in the vicinity of 22 °, it was confirmed that amorphous silica was present. From the peak position, it is considered that a portion having a crystal structure of cristobalite exists inside.
二酸化ケイ素は温度、圧力などの条件により多様な結晶構造が存在するが、クリストバライトは、立方晶系、八面体の結晶で密度が小さいことから水分を含む様々な物質を吸着する性質があるため、汚水の浄化、土壌改良及び改善、セシウム等有害物質の吸着等の効果が望める。 Silicon dioxide has various crystal structures depending on conditions such as temperature and pressure, but cristobalite has a property of adsorbing various substances including moisture because it is a cubic crystal and octahedral crystal, and its density is small. The effects of purification of sewage, soil improvement and improvement, and adsorption of harmful substances such as cesium can be expected.
塩酸処理によって得られたゲルを乾燥後、再度塩酸処理を行うか、又はそのまま５００℃で５時間焼成したゲルを作成し、さらに物性を解析した。以後、銅スラグを塩酸処理して得られたゲルを銅スラグゲル、１回目の塩酸処理により得られたゲルを乾燥したものを乾燥ゲル、再度塩酸処理して得られたゲルを塩酸処理ゲル、乾燥ゲルを焼成して得られたゲルを焼成ゲルという。 The gel obtained by the treatment with hydrochloric acid was dried and then treated with hydrochloric acid again, or a gel was baked at 500 ° C. for 5 hours as it was, and the physical properties were analyzed. Thereafter, the copper slag was treated with hydrochloric acid, the gel obtained was treated with copper slag gel, the gel obtained by the first hydrochloric acid treatment was dried, the gel obtained again with hydrochloric acid was treated with hydrochloric acid-treated gel, dried. The gel obtained by firing the gel is called fired gel.
塩酸処理ゲルは、乾燥ゲル（図４（Ａ））１ｇに対して、２０〜２００ｍｌ程度の割合で１〜６ Ｍの塩酸を添加し，室温で０．５〜３時間撹拌して得た。白い粒子の塩酸処理ゲルが生成した（図４（Ｂ））。 The hydrochloric acid-treated gel was obtained by adding 1-6 M hydrochloric acid at a rate of about 20-200 ml to 1 g of the dried gel (FIG. 4A) and stirring at room temperature for 0.5-3 hours. A white particle hydrochloric acid-treated gel was formed (FIG. 4B).
次に、銅スラグ、銅スラグゲル、乾燥ゲル、塩酸処理ゲル、焼成ゲルの組成を蛍光Ｘ線分析により解析した。結果を表４に示す。なお、表４中の数値は全体に対する重量％である。 Next, the composition of copper slag, copper slag gel, dried gel, hydrochloric acid-treated gel and fired gel was analyzed by fluorescent X-ray analysis. The results are shown in Table 4. In addition, the numerical value in Table 4 is weight% with respect to the whole.
表４から、塩酸処理ゲルは、残存していた鉄等の金属がほとんど再抽出され、二酸化ケイ素（ＳｉＯ2）が全体の９９．２質量％を占めていた。 From Table 4, in the hydrochloric acid-treated gel, most of the remaining metal such as iron was re-extracted, and silicon dioxide (SiO 2 ) accounted for 99.2% by mass of the whole.
一方、再抽出された金属は塩酸と反応して塩化物を形成しており、その主成分は塩化鉄（ＦｅＣｌ２）であった。上記塩化鉄は、大気中に放置することにより酸化されＦｅＣｌ３となる。 On the other hand, the re-extracted metal reacted with hydrochloric acid to form chloride, and its main component was iron chloride (FeCl 2 ). The iron chloride is oxidized to FeCl 3 when left in the atmosphere.
前記ＦｅＣｌ３は、銅の精錬の際に排出される排水中の微粒子に対して優れた凝集性を示すので、該排水の処理における凝集剤としての用途が期待できる。このとき、凝集剤としては高い純度は不要であり、上記塩化物をそのまま塩化鉄（ＦｅＣｌ３）として使用できるので好都合である。 Since the FeCl 3 exhibits excellent cohesiveness with respect to fine particles in waste water discharged during copper refining, it can be expected to be used as a coagulant in the treatment of the waste water. At this time, the flocculant does not require high purity and is convenient because the chloride can be used as it is as iron chloride (FeCl 3 ).
また、焼成ゲル（図４（Ｃ））は、乾燥ゲル（図４（Ａ））と比較して、粒子サイズや色調については大きな変化はなかったものの、表面に金属光沢が発現していることが目視によっても明らかに確認される。導電性を確認したところ、導電性を備えていることも確認できた。焼成ゲルには鉄が残存していることから、導電性を備えているものと考えられる。 In addition, the calcined gel (FIG. 4 (C)) does not change much in terms of particle size and color tone compared to the dried gel (FIG. 4 (A)), but has a metallic luster on the surface. Is clearly confirmed visually. As a result of confirming the conductivity, it was confirmed that the material had conductivity. Since iron remains in the fired gel, it is considered to have conductivity.
塩酸処理によって得られた乾燥ゲルを再度塩酸処理することによって、元素構成がほぼＯとＳｉであるゲルが得られたことや、焼成によって導電性ゲルが得られたので、次にこれらの物性解析を行った。 By subjecting the dried gel obtained by the hydrochloric acid treatment to hydrochloric acid treatment again, a gel whose elemental composition is almost O and Si was obtained, and a conductive gel was obtained by firing. Went.
まず、メチレンブルー吸着実験を行い、これらゲルの吸着性能の評価を行った。メチレンブルーの吸着量は、比較的分子量の大きな物質の吸着量を評価する方法として用いられている。 First, methylene blue adsorption experiments were conducted to evaluate the adsorption performance of these gels. The adsorption amount of methylene blue is used as a method for evaluating the adsorption amount of a substance having a relatively large molecular weight.
１／１５Ｍ、ｐＨ７．０のリン酸緩衝液にメチレンブルーを１２００ｍｇ／Ｌとなるように溶解し、各試料１ｇとメチレンブルー溶液２５ｍｌとを３０分間振とうし、吸引濾過した後、濾液の吸光を測定し、メチレンブルーと吸光度との相関から、濾液中に残存しているメチレンブルーの残存濃度を算出した。表５にメチレンブルーの残存濃度及び吸着量を示す。コントロールとして市販のシリカゲルを用いた。 Dissolve methylene blue to 1200 mg / L in 1 / 15M, pH 7.0 phosphate buffer, shake 1 g of each sample and 25 ml of methylene blue solution for 30 minutes, filter by suction, and then measure the absorbance of the filtrate The residual concentration of methylene blue remaining in the filtrate was calculated from the correlation between methylene blue and absorbance. Table 5 shows the residual concentration and adsorption amount of methylene blue. Commercially available silica gel was used as a control.
いずれのゲルもメチレンブルーの吸着量は、市販のシリカゲルと同程度であった。特に塩酸処置ゲルはメチレンブルーの残留濃度が低く、吸着性が良いことが示された。 All gels had the same amount of methylene blue adsorption as that of commercially available silica gel. In particular, the hydrochloric acid-treated gel showed a low residual concentration of methylene blue and good adsorptivity.
さらに、これらゲルで吸湿実験を行い、吸湿性能の評価行った。湿度５０％のもとで実験を行い、以下の式を用いて吸湿率を算出した。 Furthermore, moisture absorption experiments were conducted with these gels to evaluate the moisture absorption performance. Experiments were performed at a humidity of 50%, and the moisture absorption rate was calculated using the following equation.
吸湿率（％）＝（Ｗ１−Ｗ０）／Ｗ０×１００
（Ｗ０：乾燥した試料の質量（ｇ）、Ｗ１：吸湿後の試料の質量）
結果を表６に示す。
Moisture absorption rate (%) = (W 1 −W 0 ) / W 0 × 100
(W 0 : mass of dried sample (g), W 1 : mass of sample after moisture absorption)
The results are shown in Table 6.
表６に示すように、吸湿率は市販のシリカゲルと比較すると、焼成ゲルで同定度、乾燥ゲル、塩酸処理ゲルではシリカゲルよりも高い吸湿率であることが示された。 As shown in Table 6, it was shown that the moisture absorption rate was higher for the baked gel than for the silica gel, and for the dried gel and hydrochloric acid-treated gel, the moisture absorption rate was higher than that for the silica gel.
次に、比表面積、細孔分布及び細孔体積を測定した結果を表７に示す。試料の前処理として真空下で緩やかに加熱，排気することにより吸着水を除いた。比表面積は，吸着質を窒素とし，吸着温度７７ Ｋにおける窒素吸着量から比表面積を求める、ガス吸着ＢＥＴ法により測定した。また、吸着質が脱離するときの相対圧と吸着量の関係である脱着等温線から細孔径を求めるＢＪＨ法により、細孔径分布を測定した。 Next, Table 7 shows the results of measurement of specific surface area, pore distribution, and pore volume. As sample pretreatment, adsorbed water was removed by gently heating and evacuating under vacuum. The specific surface area was measured by a gas adsorption BET method in which the adsorbate is nitrogen and the specific surface area is obtained from the nitrogen adsorption amount at an adsorption temperature of 77 K. In addition, the pore size distribution was measured by the BJH method for obtaining the pore size from the desorption isotherm, which is the relationship between the relative pressure when the adsorbate desorbs and the amount of adsorption.
乾燥ゲルに比べ、さらに塩酸で処理することにより、比表面積が大きくなっていることが示された。塩酸で処理することにより、残存していた金属成分が抽出されるため、表面積が大きくなるものと考えられる。 It was shown that the specific surface area was increased by further treatment with hydrochloric acid as compared with the dried gel. By treating with hydrochloric acid, the remaining metal component is extracted, so the surface area is considered to be increased.
図５に、銅スラグを塩酸、又は硝酸で処理し、乾燥ゲル、焼成ゲル、又は再度塩酸処理した塩酸処理ゲル及び塩化鉄の製造方法及びその物性をまとめた。乾燥ゲル、焼成ゲル、塩酸処理ゲルはいずれも吸着性、吸湿性ともに、シリカゲルと同等以上の性質を示すことから、吸着ゲル、吸湿ゲルとして再利用できる。 In FIG. 5, the manufacturing method and the physical property of the hydrochloric acid treatment gel and iron chloride which processed copper slag with hydrochloric acid or nitric acid, and dried the gel, the baking gel, or the hydrochloric acid treatment again were put together. The dried gel, the baked gel and the hydrochloric acid-treated gel all have the same or better properties than the silica gel in both the adsorptive property and the hygroscopic property, and can be reused as the adsorbing gel and the hygroscopic gel.
また、焼成ゲルは導電性も付与されているため、新たな再利用方法も考えられる。軽質で、導電性があることから、例えば、電池材料や電極材料，ＬＣＤなどの導通材や異方性導電部材，帯電防止材，導電性塗料などに利用することが考えられる。 Moreover, since the baked gel is also provided with conductivity, a new reuse method is also conceivable. Because it is light and conductive, it can be used for battery materials, electrode materials, conductive materials such as LCD, anisotropic conductive members, antistatic materials, conductive paints, and the like.
また、本発明により生成されたケイ酸質材料は、酸素を除く元素組成は９０％以上がケイ素であり、高純度にケイ素を含有するものである。銅製錬工程には融剤としてケイ酸を使用するが、本発明のケイ酸質材料は高純度にケイ酸を含むことから、融剤として銅製錬工程での再利用も可能である。 Further, the siliceous material produced according to the present invention has silicon in an elemental composition excluding oxygen of 90% or more, and contains silicon with high purity. Although silicic acid is used as a flux in the copper smelting process, the siliceous material of the present invention contains silicic acid with high purity, so that it can be reused as a flux in the copper smelting process.
また、塩化鉄は排水処理における凝集剤として再利用できる。 Iron chloride can be reused as a flocculant in wastewater treatment.
以上示してきたように、本発明は、再利用が進まなかった銅スラグをシリカゲルと同等の、あるいは導電性を備えたゲルとして使用する新しい再利用方法を示すものである。これにより、今まで限られた利用方法しかなく、再利用が進まず堆積保管されていた銅スラグを有効に再利用することが可能となる。特に銅製錬工程での再利用は、銅製錬プロセスから出た銅スラグを再度製錬プロセスに組み入れるものであるとともに、比較的多量の再利用が見込まれることから、有効な再利用方法である。 As described above, the present invention shows a new recycling method in which copper slag, which has not been reused, is used as a gel equivalent to or having conductivity with silica gel. As a result, there is only a limited utilization method so far, and it is possible to effectively reuse the copper slag that has been deposited and stored without being reused. In particular, reuse in the copper smelting process is an effective reuse method because copper slag from the copper smelting process is incorporated into the smelting process again and a relatively large amount of reuse is expected.
Claims (9)
銅スラグを塩酸又は硝酸を含む水溶液で処理することによって、ヒドロゲルを生成し、
前記ヒドロゲルを乾燥することを特徴とするケイ酸質材料の製造方法。 A method for producing a siliceous material containing silicic acid with high purity produced from copper smelting slag,
A hydrogel is produced by treating copper slag with an aqueous solution containing hydrochloric acid or nitric acid,
A method for producing a siliceous material, wherein the hydrogel is dried.
請求項１〜３のいずれか１項記載のケイ酸質材料を銅製錬工程の融剤として再利用することを特徴とするケイ酸質材料の使用方法。 A method of using a siliceous material containing silicic acid in high purity produced from copper smelting slag,
A method for using a siliceous material, wherein the siliceous material according to any one of claims 1 to 3 is reused as a flux in a copper smelting process.
銅製錬スラグを塩酸又は硝酸を含む水溶液で処理し、乾燥することによって製造することを特徴とするケイ酸質材料。 A siliceous material containing high-purity silicic acid produced from copper smelting slag,
A siliceous material produced by treating copper smelting slag with an aqueous solution containing hydrochloric acid or nitric acid and drying.
請求項６記載のケイ酸質材料を焼成することによって製造することを特徴とするケイ酸質材料。 A siliceous material containing high-purity silicic acid produced from copper smelting slag,
A siliceous material produced by firing the siliceous material according to claim 6.
請求項６記載のケイ酸質材料を酸浸出することによって製造することを特徴とするケイ酸質材料。 A siliceous material containing high-purity silicic acid produced from copper smelting slag,
A siliceous material produced by acid leaching of the siliceous material according to claim 6.
請求項６記載のケイ酸質材料を塩酸浸出することによって製造することを特徴とする凝集剤。 A flocculant as a by-product of high-purity siliceous material produced from copper smelting slag,
A flocculant produced by leaching the siliceous material according to claim 6 with hydrochloric acid.
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