JP6644804B2 - Adsorbent particles and granulated adsorbent - Google Patents
Adsorbent particles and granulated adsorbent Download PDFInfo
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- JP6644804B2 JP6644804B2 JP2017544197A JP2017544197A JP6644804B2 JP 6644804 B2 JP6644804 B2 JP 6644804B2 JP 2017544197 A JP2017544197 A JP 2017544197A JP 2017544197 A JP2017544197 A JP 2017544197A JP 6644804 B2 JP6644804 B2 JP 6644804B2
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- 239000003463 adsorbent Substances 0.000 title claims description 180
- 239000002245 particle Substances 0.000 title claims description 127
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 65
- 238000001179 sorption measurement Methods 0.000 claims description 60
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 47
- 150000001450 anions Chemical class 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000011574 phosphorus Substances 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 12
- 150000002484 inorganic compounds Chemical group 0.000 claims description 11
- 229910010272 inorganic material Inorganic materials 0.000 claims description 11
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 11
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 11
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 229920005672 polyolefin resin Polymers 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 230000035699 permeability Effects 0.000 claims description 3
- 229940085991 phosphate ion Drugs 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 claims description 2
- 229940005631 hypophosphite ion Drugs 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical compound [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000000034 method Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- -1 phosphorus compound Chemical class 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000001747 exhibiting effect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 150000002506 iron compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NYZDKUUYFWLHQF-UHFFFAOYSA-N O(O)O.[O-2].[Fe+2] Chemical compound O(O)O.[O-2].[Fe+2] NYZDKUUYFWLHQF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
Description
本発明は、オキシ水酸化鉄を主成分とする吸着材粒子、及び該吸着材粒子とバインダーとからなる造粒吸着材に関する。
本願は、２０１５年１０月９日に出願された日本国特許出願第２０１５−２００７３６号に対し優先権を主張し、その内容をここに援用する。The present invention relates to an adsorbent particle containing iron oxyhydroxide as a main component, and a granulated adsorbent comprising the adsorbent particle and a binder.
This application claims priority to Japanese Patent Application No. 2015-200736 for which it applied on October 9, 2015, and uses the content here.
各種の排水から、環境や人体に有害性を有する物質を除去し浄化するため、あるいは希少金属等の有用物質を回収するために、吸着材や、それを用いた吸着方法、吸着物質の脱着・回収方法等が盛んに研究されている。
例えば、リンは肥料成分として、また化学工業にも不可欠の成分であるが、日本においてはほぼ１００％を輸入に頼っている。一方で排水中に多量のリンが含まれる場合は、富栄養化の原因となるため、このような排水を排出することは環境に好ましくない。これらの問題を一挙に解決するために、排水中に含まれるリン酸等のリン化合物の除去及び回収が注目されている。
このようなリン化合物を効率的に吸着、回収できる吸着材として、オキシ水酸化鉄からなるものが開発されており、特許文献１、２、３等に記載されている。
特許文献４等には、砒素吸着材として、平均粒子径０．１〜５０μｍ程度でＢＥＴ比表面積が２０〜１００ｍ2／ｇのゲーサイト（α−オキシ水酸化鉄）が記載されている。
また特殊な構造を有するオキシ水酸化鉄吸着材として、特許文献５には、水酸化鉄マトリックス中に埋め込まれたオキシ水酸化鉄からなる粒状の吸着媒体、また特許文献６には、オキシ水酸化鉄からなる多孔性の粒状凝集物が記載されているが、これらは反復使用するための取扱いには困難がある。
特許文献７には、結着剤として酸化チタンゾルを用い、ゲーサイト（α−ＦｅＯＯＨ）を造粒してなるリン吸着材が記載されている。In order to remove and purify substances that are harmful to the environment and the human body from various types of wastewater, or to recover useful substances such as rare metals, adsorbents, adsorption methods using them, and desorption / The collection method is being actively studied.
For example, phosphorus is an indispensable component in fertilizers and in the chemical industry, but in Japan almost 100% relies on imports. On the other hand, if a large amount of phosphorus is contained in the wastewater, it causes eutrophication, and it is not preferable for the environment to discharge such wastewater. In order to solve these problems at once, attention has been paid to the removal and recovery of phosphorus compounds such as phosphoric acid contained in wastewater.
As an adsorbent capable of efficiently adsorbing and recovering such a phosphorus compound, an adsorbent composed of iron oxyhydroxide has been developed and described in Patent Documents 1, 2, and 3 and the like.
Patent Document 4 and the like describe, as an arsenic adsorbent, goethite (α-iron oxyhydroxide) having an average particle diameter of about 0.1 to 50 μm and a BET specific surface area of 20 to 100 m 2 / g.
As an iron oxyhydroxide adsorbent having a special structure, Patent Document 5 discloses a granular adsorption medium comprising iron oxyhydroxide embedded in an iron hydroxide matrix, and Patent Document 6 discloses an iron oxyhydroxide adsorbent. Although porous granular agglomerates of iron are described, they are difficult to handle for repeated use.
Patent Literature 7 describes a phosphorus adsorbent obtained by granulating goethite (α-FeOOH) using titanium oxide sol as a binder.
吸着材において、短時間で高い吸着効率を得るには、材料として多孔質の吸着材を用いるとともに、吸着材の粒子径を小さくすることが望ましい。しかし、粒子径が１μｍ程度以下の吸着材を液中で使用すると、分離、回収が容易でなく、実用的ではなかった。 In order to obtain high adsorption efficiency in a short time in the adsorbent, it is desirable to use a porous adsorbent as a material and reduce the particle diameter of the adsorbent. However, when an adsorbent having a particle diameter of about 1 μm or less is used in a liquid, separation and recovery are not easy and not practical.
本発明者は、オキシ水酸化鉄からなる吸着材において、高い吸着効率と、吸着材の容易な分離とを両立させるべく多面的に鋭意検討した。
その結果、吸着材を粉砕した上で特定の粒径範囲の粒子を回収することにより、従来品に比較して短時間で高い吸着効率を発揮し、しかも吸着後の回収が容易であり反復使用に適した吸着材が得られることを見出した。
また、オキシ水酸化鉄からなる上記粒子と同じオキシ水酸化鉄からなるナノ分散液とを混合し、乾燥することにより、大粒径で取扱いが容易でありながら高い吸着効率を発揮する吸着材が得られることを見出した。本発明は以上の知見を元に完成されたものである。The inventor of the present invention has intensively studied various aspects of an adsorbent made of iron oxyhydroxide in order to achieve both high adsorption efficiency and easy separation of the adsorbent.
As a result, by collecting the particles in a specific particle size range after crushing the adsorbent, higher adsorption efficiency can be demonstrated in a shorter time than conventional products, and the collection after adsorption is easy and repeated use. It has been found that a suitable adsorbent can be obtained.
In addition, by mixing the above particles composed of iron oxyhydroxide with the nano-dispersion liquid composed of the same iron oxyhydroxide, and drying the mixture, an adsorbent exhibiting a large particle diameter and exhibiting high adsorption efficiency while being easy to handle is obtained. It was found that it could be obtained. The present invention has been completed based on the above findings.
すなわち、本発明は、以下の発明に関する。
（１）平均粒径ｄ５０が１０〜７０μｍである、オキシ水酸化鉄を主成分とする吸着材粒子。
（２）前記オキシ水酸化鉄がβ−オキシ水酸化鉄である、（１）に記載の吸着材粒子。
（３）陰イオン吸着材である、（１）又は（２）に記載の吸着材粒子。
（４）平均結晶子径が１０ｎｍ以下である、（１）〜（３）のいずれかに記載の吸着材粒子。
（５）結晶の形状が粒状である、（４）に記載の吸着材粒子。
（６）塩酸でｐＨを３．５に調整したリン換算濃度４００ｍｇ／Ｌのリン酸二水素カリウム水溶液１５０ｍＬ中に吸着材粒子１ｇを投入し、室温で撹拌して行う回分式の吸着試験において、１時間後に吸着材１ｇ当たりのリン換算吸着量が２２ｍｇ以上である、（３）〜（５）のいずれかに記載の吸着材粒子。
（７）塩酸でｐＨを３．５に調整したリン換算濃度４００ｍｇ／Ｌのリン酸二水素カリウム水溶液１５０ｍＬ中に吸着材粒子１ｇを投入し、室温で撹拌して行う回分式の試験において、１時間後のｐＨに対し、２４時間後のｐＨが０．５以上上昇することを特徴とする、（３）〜（６）のいずれかに記載の吸着材粒子。
（８）オキシ水酸化鉄を主成分とする固体を粉砕し、該粉砕物を水中において５〜２０μｍの目開きを有するメッシュで分級し、メッシュを通過しない分を回収して得られる吸着材粒子の製造方法。
（９）（１）〜（７）のいずれかに記載の吸着材粒子とバインダーとを含有する、粒径０．１ｍｍ以上の造粒吸着材。
（１０）バインダーがｐＨ２．５〜１２．５の範囲で安定である、（９）に記載の造粒吸着材。
（１１）吸着材とバインダーとの質量比が、２：１〜１００：１である、（９）又は（１０）に記載の造粒吸着材。
（１２）バインダーが無機化合物である、（１０）又は（１１）に記載の造粒吸着材。
（１３）無機化合物が、鉄、ジルコニウム、チタン及びスズから選ばれる少なくとも１種の金属の化合物である、（１２）に記載の造粒吸着材。
（１４）無機化合物がオキシ水酸化鉄を主成分とする、（１３）に記載の造粒吸着材。
（１５）バインダーがポリオレフィン系樹脂である、（９）〜（１１）のいずれかに記載の造粒吸着材。
（１６）陰イオン吸着材である、（９）〜（１５）のいずれかに記載の造粒吸着材。
（１７）塩酸でｐＨを３．５に調整したリン換算濃度４００ｍｇ／Ｌのリン酸二水素カリウム水溶液１５０ｍＬ中に造粒吸着材１ｇを投入し、室温で撹拌して行う回分式の吸着試験において、１時間後に吸着材１ｇ当たりのリン換算吸着量が２２ｍｇ以上である、（１６）に記載の造粒吸着材。
（１８）塩酸でｐＨを３．５に調整したリン換算濃度４００ｍｇ／Ｌのリン酸二水素カリウム水溶液１５０ｍＬ中に造粒吸着材１ｇを投入し、室温で撹拌して行う回分式の試験において、１時間後のｐＨに対し、２４時間後のｐＨが０．５以上上昇することを特徴とする、（１６）又は（１７）に記載の造粒吸着材。
（１９）（１）〜（７）のいずれかに記載の吸着材粒子と、バインダーとを造粒する工程を含む、造粒吸着材の製造方法。
（２０）（１）〜（７）のいずれかに記載の吸着材粒子、又は（９）〜（１８）のいずれかに記載の造粒吸着材を、通水性を有し該吸着材粒子又は造粒吸着材を通さない容器に収納してなる、吸着材。That is, the present invention relates to the following inventions.
(1) Adsorbent particles containing iron oxyhydroxide as a main component and having an average particle size d50 of 10 to 70 μm.
(2) The adsorbent particles according to (1), wherein the iron oxyhydroxide is β-iron oxyhydroxide.
(3) The adsorbent particles according to (1) or (2), which are anion adsorbents.
(4) The adsorbent particles according to any one of (1) to (3), wherein the average crystallite diameter is 10 nm or less.
(5) The adsorbent particles according to (4), wherein the crystal has a granular shape.
(6) In a batch-type adsorption test in which 1 g of adsorbent particles are put into 150 mL of an aqueous solution of potassium dihydrogen phosphate having a concentration in terms of phosphorus of 400 mg / L adjusted to pH 3.5 with hydrochloric acid and stirred at room temperature, The adsorbent particles according to any one of (3) to (5), wherein after 1 hour, the amount of adsorption in terms of phosphorus per gram of the adsorbent is 22 mg or more.
(7) In a batch test, 1 g of the adsorbent particles was put into 150 mL of an aqueous solution of potassium dihydrogen phosphate having a concentration of 400 mg / L in terms of phosphorus adjusted to pH 3.5 with hydrochloric acid and stirred at room temperature. The adsorbent particles according to any one of (3) to (6), wherein the pH after 24 hours is increased by 0.5 or more with respect to the pH after time.
(8) Adsorbent particles obtained by crushing a solid containing iron oxyhydroxide as a main component, classifying the crushed product in water with a mesh having a mesh size of 5 to 20 μm, and collecting a portion that does not pass through the mesh. Manufacturing method.
(9) A granulated adsorbent having a particle diameter of 0.1 mm or more, comprising the adsorbent particles according to any one of (1) to (7) and a binder.
(10) The granulated adsorbent according to (9), wherein the binder is stable in a pH range of 2.5 to 12.5.
(11) The granulated adsorbent according to (9) or (10), wherein the mass ratio between the adsorbent and the binder is 2: 1 to 100: 1.
(12) The granulated adsorbent according to (10) or (11), wherein the binder is an inorganic compound.
(13) The granulated adsorbent according to (12), wherein the inorganic compound is a compound of at least one metal selected from iron, zirconium, titanium and tin.
(14) The granulated adsorbent according to (13), wherein the inorganic compound contains iron oxyhydroxide as a main component.
(15) The granulated adsorbent according to any one of (9) to (11), wherein the binder is a polyolefin-based resin.
(16) The granulated adsorbent according to any one of (9) to (15), which is an anion adsorbent.
(17) In a batch-type adsorption test in which 1 g of a granulated adsorbent is put into 150 mL of an aqueous solution of potassium dihydrogen phosphate having a concentration in terms of phosphorus of 400 mg / L adjusted to a pH of 3.5 with hydrochloric acid and stirred at room temperature. (16) The granulated adsorbent according to (16), wherein the amount of adsorption in terms of phosphorus per gram of the adsorbent after 1 hour is 22 mg or more.
(18) In a batch-type test, 1 g of the granulated adsorbent was put into 150 mL of an aqueous solution of potassium dihydrogen phosphate having a concentration in terms of phosphorus of 400 mg / L adjusted to a pH of 3.5 with hydrochloric acid and stirred at room temperature. The granulated adsorbent according to (16) or (17), wherein the pH after 24 hours is increased by 0.5 or more with respect to the pH after 1 hour.
(19) A method for producing a granulated adsorbent, comprising a step of granulating the adsorbent particles according to any one of (1) to (7) and a binder.
(20) The adsorbent particles according to any one of (1) to (7) or the granulated adsorbent according to any one of (9) to (18), An adsorbent housed in a container that does not allow the granulated adsorbent to pass through.
吸着材を粉砕した上で特定の粒径範囲の粒子を回収することにより、従来品に比較して短時間で高い吸着効率を発揮し、しかも吸着後の回収が容易であり反復使用に適した吸着材が得られる。
また、オキシ水酸化鉄からなる上記粒子と同じオキシ水酸化鉄からなるナノ分散液とを混合し、乾燥することにより、大粒径で取扱いが容易でありながら高い吸着効率を発揮する吸着材が得られる。By collecting particles in a specific particle size range after crushing the adsorbent, it exhibits high adsorption efficiency in a short time compared to conventional products, and is easy to collect after adsorption, making it suitable for repeated use An adsorbent is obtained.
In addition, by mixing the above particles composed of iron oxyhydroxide with the nano-dispersion liquid composed of the same iron oxyhydroxide, and drying the mixture, an adsorbent exhibiting a large particle diameter and exhibiting high adsorption efficiency while being easy to handle is obtained. can get.
（吸着材粒子）
本発明の吸着材粒子は、
ｉ）平均粒径ｄ５０が１０〜７０μｍである、オキシ水酸化鉄を主成分とする吸着材粒子、
ｉｉ）鉄化合物含有溶液を塩基と反応させ沈殿物を生成させる工程を含む方法により生成した、オキシ水酸化鉄を主成分とする乾燥ゲルからなり、平均粒径ｄ５０が１０〜７０μｍである吸着材粒子、又は
ｉｉｉ）オキシ水酸化鉄を主成分とする固体を粉砕し、該粉砕物を水中において５〜２０μｍの目開きを有するメッシュで分級し、メッシュを通過しない分を回収して得られる、吸着材粒子である。
本発明の吸着材粒子の平均粒径（ｄ５０）は、３０〜７０μｍであることがより好ましい。さらに本発明の吸着材粒子のｄ１０は、５μｍ以上であることが好ましい。(Adsorbent particles)
The adsorbent particles of the present invention,
i) adsorbent particles containing iron oxyhydroxide as a main component, having an average particle diameter d50 of 10 to 70 μm;
ii) an adsorbent made of a dried gel containing iron oxyhydroxide as a main component and having an average particle diameter d50 of 10 to 70 μm, which is produced by a method including a step of reacting a solution containing an iron compound with a base to form a precipitate. Particles, or iii) crushing a solid containing iron oxyhydroxide as a main component, classifying the crushed product in water with a mesh having an opening of 5 to 20 μm, and collecting a portion that does not pass through the mesh. Adsorbent particles.
The average particle diameter (d50) of the adsorbent particles of the present invention is more preferably 30 to 70 μm. Further, d10 of the adsorbent particles of the present invention is preferably 5 μm or more.
オキシ水酸化鉄は、陰イオンに対する吸着性に優れている。
本発明の吸着材粒子は、主成分オキシ水酸化鉄の含有率が９９質量％以上であることが好ましい。オキシ水酸化鉄の含有率が実質的に１００質量％であるものが最も好ましい。
オキシ水酸化鉄には、結晶構造の相違によって、α型、β型、γ型、非晶質型等がある。これらのうち、β−オキシ水酸化鉄が、吸着性能の点で特に優れており、リン酸イオン、亜リン酸イオン、次亜リン酸イオン、硫酸イオン、硝酸イオン、フッ化物イオン等の吸着材に適している。
本発明の吸着材粒子としても、このβ−オキシ水酸化鉄を主成分とするものが好ましい。
β−オキシ水酸化鉄は、一般に、水酸基の一部が塩素イオンにより置換されている。製造又は使用の過程で水と接触すると、この塩素イオンが回収されて小型の空孔が残る。この空孔がフッ素等の陰イオンの吸着に関与すると考えられており、さらに本発明における効率的な陰イオン吸着もこの空孔に由来する特徴であると考えられる。
本発明におけるオキシ水酸化鉄は、β−オキシ水酸化鉄であることが好ましい。さらにβ−オキシ水酸化鉄中における塩素イオンの含有量は、０．５質量％以上であることが好ましく、３質量％以上であることがより好ましい。Iron oxyhydroxide has excellent adsorptivity to anions.
It is preferable that the content of the main component iron oxyhydroxide in the adsorbent particles of the present invention is 99% by mass or more. Most preferably, the content of iron oxyhydroxide is substantially 100% by mass.
Iron oxyhydroxide includes α-type, β-type, γ-type, and amorphous type depending on the crystal structure. Among these, β-iron oxyhydroxide is particularly excellent in terms of adsorption performance, and adsorbents such as phosphate ion, phosphite ion, hypophosphite ion, sulfate ion, nitrate ion, and fluoride ion Suitable for.
As the adsorbent particles of the present invention, those containing β-iron oxyhydroxide as a main component are preferable.
β-iron oxyhydroxide generally has a part of hydroxyl groups replaced by chloride ions. When it comes into contact with water during the production or use process, this chloride ion is recovered, leaving small pores. It is considered that the vacancies are involved in the adsorption of anions such as fluorine, and the efficient anion adsorption in the present invention is also considered to be a feature derived from the vacancies.
The iron oxyhydroxide in the present invention is preferably β-iron oxyhydroxide. Further, the content of chlorine ions in β-iron oxyhydroxide is preferably 0.5% by mass or more, more preferably 3% by mass or more.
本発明の吸着材粒子の製造方法としては、必ずしも限定されるものではないが、オキシ水酸化鉄を主成分とする固体を粉砕し、該粉砕物を水中において５〜２０μｍの目開きを有するメッシュで分級し、メッシュを通過しない分を回収する方法が挙げられる。 The method for producing the adsorbent particles of the present invention is not particularly limited, but a solid having iron oxide oxyhydroxide as a main component is pulverized, and the pulverized product is meshed with 5 to 20 μm mesh in water. And a method of collecting a portion not passing through the mesh.
前記のオキシ水酸化鉄を主成分とする固体としては、鉄化合物含有溶液を塩基と反応させｐＨ９以下で沈殿物を生成させる工程を含む方法により得られる乾燥ゲルが好ましい。
前記の鉄化合物としては、鉄塩、特に３価の鉄塩が好ましい。具体的には、塩化第二鉄、硫酸第二鉄、硝酸第二鉄等を挙げることができ、この中で特に塩化第二鉄が好ましい。
前記の塩基は、酸性の鉄化合物水溶液を中和しオキシ水酸化鉄を含む沈殿を生成させるために使用する。具体的には、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、アンモニア、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム等を挙げることができ、この中で特に水酸化ナトリウムが好ましい。
沈殿物の生成の際のｐＨは、ｐＨ３．３〜６の範囲に調整することがより好ましい。
以上の方法で得られたオキシ水酸化鉄を主成分とする沈殿物は、濾別して回収することができ、これを乾燥すれば乾燥ゲルとなる。As the solid containing iron oxyhydroxide as a main component, a dried gel obtained by a method including a step of reacting an iron compound-containing solution with a base to form a precipitate at pH 9 or less is preferable.
As the iron compound, an iron salt, particularly, a trivalent iron salt is preferable. Specific examples include ferric chloride, ferric sulfate, and ferric nitrate. Of these, ferric chloride is particularly preferred.
The base is used to neutralize the aqueous solution of the acidic iron compound and generate a precipitate containing iron oxyhydroxide. Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium carbonate, potassium carbonate, calcium carbonate, and the like. Of these, sodium hydroxide is particularly preferred.
It is more preferable that the pH at the time of generation of the precipitate is adjusted to a range of pH 3.3 to 6.
The precipitate containing iron oxyhydroxide as a main component obtained by the above method can be collected by filtration and dried to form a dried gel.
さらに以上の工程の後に、沈殿物を乾燥させる工程、及び該乾燥物を水と接触させた後、乾燥させる工程を実施することが好ましい。
上記２回の乾燥をさせる工程は、１４０℃以下で行うことが好ましく、１００〜１４０℃で行うことがより好ましい。乾燥温度は、低温では時間を要し効率的な製造に適しない。また高温では陰イオン吸着サイトが少なくなる傾向があり、さらに高温では酸化鉄に変化するので好ましくない。乾燥は、空気中、真空中、又は不活性ガス中で行うことができる。
乾燥物を水と接触させる工程では、塩化ナトリウム等の不純物が溶出して後に細孔を残し、比表面積が増大するとともに陰イオン吸着サイトも増加すると考えられる。
乾燥物を水と接触させた後、水を回収して、再度乾燥させる。この乾燥工程も上記と同様の条件で行うことが好ましい。
以上の方法により得られる乾燥ゲルは、β−オキシ水酸化鉄を主成分として含む。Further, after the above steps, it is preferable to carry out a step of drying the precipitate, and a step of bringing the dried substance into contact with water and then drying.
The two drying steps are preferably performed at 140 ° C. or lower, more preferably at 100 to 140 ° C. The drying temperature takes a long time at a low temperature, and is not suitable for efficient production. At high temperatures, the number of anion adsorption sites tends to decrease, and further at high temperatures, it changes to iron oxide, which is not preferable. Drying can be performed in air, in a vacuum, or in an inert gas.
In the step of bringing the dried product into contact with water, it is considered that impurities such as sodium chloride are eluted and pores are left behind, and the specific surface area increases and the number of anion adsorption sites increases.
After the dried product is brought into contact with water, the water is recovered and dried again. This drying step is also preferably performed under the same conditions as described above.
The dried gel obtained by the above method contains β-iron oxyhydroxide as a main component.
本発明の吸着材粒子の主成分であるオキシ水酸化鉄は、ＢＥＴ比表面積が２００ｍ2／ｇ以上であることが好ましく、またＢＪＨ法により算出した細孔容量の面積分布（ｄＶ／ｄＲ）が１００〜３００ｍｍ3／ｇ／ｎｍであることが好ましい。The iron oxyhydroxide, which is the main component of the adsorbent particles of the present invention, preferably has a BET specific surface area of 200 m 2 / g or more, and has a pore volume area distribution (dV / dR) calculated by the BJH method. It is preferably from 100 to 300 mm 3 / g / nm.
本発明の吸着材粒子の製造工程で、オキシ水酸化鉄を主成分とする固体を粉砕する場合、乾式粉砕を用いることが好ましい。
また本発明の吸着材粒子の製造工程では、粒径を適切な範囲とするために、メッシュによる分級を行うことが好ましい。
この分級の方法としては、該粉砕物を水中において５〜２０μｍの目開きを有するメッシュで分級し、メッシュを通過しない分を回収する方法が簡便で好ましい。このメッシュの目開きとしては、１０μｍが特に好ましい。When pulverizing a solid mainly composed of iron oxyhydroxide in the production process of the adsorbent particles of the present invention, it is preferable to use dry pulverization.
In addition, in the production process of the adsorbent particles of the present invention, it is preferable to perform classification using a mesh in order to control the particle size to an appropriate range.
As a method for this classification, a method in which the pulverized material is classified in water with a mesh having a mesh size of 5 to 20 μm, and a portion that does not pass through the mesh is recovered is simple and preferable. The mesh opening is particularly preferably 10 μm.
本発明の吸着材粒子は、気相中で、例えば排ガス中の有害物質等を吸着するために使用することもできるが、液相中で使用することがより好ましい。
一般に、液相中で吸着材を使用する場合、液体に含まれる成分が拡散により細孔中に達するには時間を要するため、吸着平衡に達するのには時間を要する。
本発明の吸着材粒子は、従来の吸着材に比較して、一定量の吸着に要する時間を大幅に短縮し、これにより効率的な吸着を行うことができる。
上記の液相としては、吸着材以外の部分が均一な液相であれば問題なく使用可能であり、例えば有機溶媒溶液も用いることができるが、前記課題として記載したように、有害物質の回収、有用物質の回収等を目的として、水溶液中で使用することが好ましい。
また、本発明の吸着材粒子は、液相を撹拌すれば分散し、液相を静置すれば速やかに沈降して容易に回収できるものであるから、流動床において使用するのに特に適している。The adsorbent particles of the present invention can be used in a gas phase, for example, for adsorbing harmful substances in exhaust gas, but are more preferably used in a liquid phase.
Generally, when an adsorbent is used in a liquid phase, it takes time for the components contained in the liquid to reach the pores by diffusion, so that it takes time to reach adsorption equilibrium.
The adsorbent particles of the present invention can significantly reduce the time required for a certain amount of adsorption as compared with conventional adsorbents, thereby enabling efficient adsorption.
As the above liquid phase, any portion other than the adsorbent can be used without any problem as long as it is a uniform liquid phase. For example, an organic solvent solution can also be used. It is preferably used in an aqueous solution for the purpose of recovering useful substances.
In addition, the adsorbent particles of the present invention are particularly suitable for use in a fluidized bed because the adsorbent particles are dispersed when the liquid phase is stirred, and can be quickly settled and recovered easily when the liquid phase is allowed to stand. I have.
本発明の吸着材粒子は、結晶の形状が粒状であることが好ましい。ここで粒状とは、針状あるいは板状ではないということを意味し、より具体的には、結晶の長径／短径の比が３以下である。 The adsorbent particles of the present invention preferably have a crystalline crystal shape. Here, “granular” means that the crystal is not needle-like or plate-like, and more specifically, the ratio of the major axis / minor axis of the crystal is 3 or less.
本発明の吸着材粒子は、平均結晶子径が１０ｎｍ以下であることが好ましく、５ｎｍ以下であることがより好ましい。
この平均結晶子径が小さいほど、水中でリン酸吸着材として使用する場合のリン酸吸着速度が大きいことが、本発明者らにより明らかにされた。
平均結晶子径Ｄは、Ｘ線回折でβ−オキシ水酸化鉄に特徴的な２θ＝３５°付近の回折線から、下記のシェラーの式を用いて計算される。
Ｄ＝Ｋλ／βｃｏｓθ
ただし、βは装置に起因する機械幅を補正した真の回折ピークの半値幅、Ｋはシェラー定数、λはＸ線の波長である。The adsorbent particles of the present invention preferably have an average crystallite diameter of 10 nm or less, more preferably 5 nm or less.
The present inventors have clarified that the smaller the average crystallite diameter, the higher the phosphoric acid adsorption rate when used as a phosphoric acid adsorbent in water.
The average crystallite diameter D is calculated from the diffraction line near 2θ = 35 ° characteristic of β-iron oxyhydroxide by X-ray diffraction using the following Scherrer equation.
D = Kλ / βcosθ
Here, β is the full width at half maximum of the true diffraction peak corrected for the mechanical width caused by the apparatus, K is the Scherrer constant, and λ is the wavelength of the X-ray.
（造粒吸着材）
本発明の吸着材粒子は、そのまま吸着材として使用するほかに、新たな吸着材を製造する材料として使用することができる。
例えば、適切なバインダーを用いて、本発明の吸着材粒子どうしを結合し造粒することにより、該吸着材粒子と同等の吸着性能を有しながら、より大きなサイズを有し取り扱いの容易な吸着材（造粒吸着材）を製造することができる。この造粒吸着材は、粒径が０．１ｍｍ以上であることが好ましく、０．２５ｍｍ以上であることがより好ましい。
また、他種の吸着材と結合することにより、本発明の吸着材粒子と異なる性能を有する吸着材を製造することも可能である。(Granulation adsorbent)
The adsorbent particles of the present invention can be used as a material for producing a new adsorbent in addition to being used as an adsorbent as it is.
For example, by adsorbing the adsorbent particles of the present invention using an appropriate binder and granulating the adsorbent particles, the adsorbent particles have an adsorption performance equivalent to that of the adsorbent particles, but have a larger size and are easily handled. A material (granulated adsorbent) can be manufactured. The particle size of the granulated adsorbent is preferably 0.1 mm or more, more preferably 0.25 mm or more.
In addition, it is also possible to produce an adsorbent having performance different from that of the adsorbent particles of the present invention by combining with other types of adsorbents.
前記バインダーは、ｐＨ２．５〜１２．５の範囲で安定であることが好ましい。後述のように、陰イオンを脱着させる際にはアルカリ性にする必要があるので、バインダーはｐＨ２．５〜１４の範囲で安定であることがより好ましい。
また、吸着材粒子とバインダーとの質量比は、２：１〜１００：１であることが好ましく、２：１〜２０：１であることがより好ましく、４：１〜９：１であることが特に好ましい。The binder is preferably stable in the range of pH 2.5 to 12.5. As described later, it is necessary to make the binder alkaline when desorbing anions. Therefore, the binder is more preferably stable in a pH range of 2.5 to 14.
The mass ratio between the adsorbent particles and the binder is preferably from 2: 1 to 100: 1, more preferably from 2: 1 to 20: 1, and preferably from 4: 1 to 9: 1. Is particularly preferred.
またバインダーは、吸着材の表面を覆うことによって吸着性能を下げるものであってはならない。
バインダーの材質は、以上の条件に合致すれば特に限定されないが、例えば無機化合物を用いることができる。無機化合物は一般に粒子状の形状をとるため、吸着材の表面を覆うことが少なく、バインダーに適している。
バインダーが無機化合物である場合、その一次粒子径が０．１μｍ以下のものが好ましい。この場合には、該粒子が液中に分散してなる分散液を用いて、造粒吸着物を製造することが好ましい。
また、無機化合物であるバインダー自体が吸着材であってもよい。Also, the binder should not reduce the adsorption performance by covering the surface of the adsorbent.
The material of the binder is not particularly limited as long as it satisfies the above conditions. For example, an inorganic compound can be used. Since the inorganic compound generally has a particulate shape, it does not cover the surface of the adsorbent, and is suitable for a binder.
When the binder is an inorganic compound, those having a primary particle diameter of 0.1 μm or less are preferable. In this case, it is preferable to produce a granulated adsorbate using a dispersion liquid in which the particles are dispersed in a liquid.
Further, the binder itself, which is an inorganic compound, may be the adsorbent.
前記無機化合物としては、鉄、ジルコニウム、チタン及びスズから選ばれる金属の化合物が例示される。特に、上掲の金属の酸化物又は水酸化物が好ましい。
このうち特に、オキシ水酸化鉄を主成分とすることが好ましい。バインダーにおけるオキシ水酸化鉄の含有率は、前述の本発明の吸着材粒子と同様、９９質量％以上であることが好ましく、オキシ水酸化鉄の含有率が実質的に１００質量％であるものが最も好ましい。
オキシ水酸化鉄は、リン酸イオン、亜リン酸イオン、次亜リン酸イオン、硝酸イオン、フッ化物イオン等に対する吸着性に優れている。
オキシ水酸化鉄には、結晶構造の相違によって、α−オキシ水酸化鉄、β−オキシ水酸化鉄、γ−オキシ水酸化鉄、又は非晶質オキシ水酸化鉄がある。これらのうち、β−オキシ水酸化鉄の吸着性能が特に優れている。
本発明に用いるオキシ水酸化鉄は、ＢＥＴ比表面積が２００ｍ2／ｇ以上であることが好ましく、またＢＪＨ法により算出した細孔容量の面積分布（ｄＶ／ｄＲ）が１００〜３００ｍｍ3／ｇ／ｎｍであることが好ましい。Examples of the inorganic compound include compounds of metals selected from iron, zirconium, titanium and tin. In particular, the above-mentioned metal oxides or hydroxides are preferable.
Among them, it is particularly preferable to use iron oxyhydroxide as a main component. The content of iron oxyhydroxide in the binder is preferably 99% by mass or more, as in the case of the above-described adsorbent particles of the present invention, and the content of iron oxyhydroxide is substantially 100% by mass. Most preferred.
Iron oxyhydroxide has excellent adsorptivity to phosphate ions, phosphite ions, hypophosphite ions, nitrate ions, fluoride ions and the like.
The iron oxyhydroxide includes α-iron oxyhydroxide, β-iron oxyhydroxide, γ-iron oxyhydroxide, or amorphous iron oxyhydroxide depending on the crystal structure. Among these, the adsorption performance of β-iron oxyhydroxide is particularly excellent.
The iron oxyhydroxide used in the present invention preferably has a BET specific surface area of 200 m 2 / g or more, and has a pore volume area distribution (dV / dR) calculated by the BJH method of 100 to 300 mm 3 / g / g. It is preferably nm.
本発明の造粒吸着材は、気相中で使用することもできるが、液相中で使用することが好ましい。
一般に、液相中で吸着材を使用する場合、液体に含まれる成分が拡散により細孔中に達するには時間を要するため、吸着平衡に達するのには時間を要する。一方吸着材をナノ粒子として液中に分散させれば速やかに吸着平衡に達するが、ナノ粒子の分離、回収に問題がある。本発明の造粒吸着材は、これらの問題を同時に解決する目的を有するものであるから、液相中で使用するのに特に適している。
上記の液相としては、造粒吸着材以外の部分が均一な液相であれば問題なく使用可能であり、例えば有機溶媒溶液も用いることができるが、前記課題として記載したように、有害物質の回収、有用物質の回収等を目的として、水溶液中で使用することが好ましい。The granulated adsorbent of the present invention can be used in a gas phase, but is preferably used in a liquid phase.
Generally, when an adsorbent is used in a liquid phase, it takes time for the components contained in the liquid to reach the pores by diffusion, so that it takes time to reach adsorption equilibrium. On the other hand, if the adsorbent is dispersed in the liquid as nanoparticles, the adsorption equilibrium is quickly reached, but there is a problem in the separation and recovery of the nanoparticles. The granulated adsorbent of the present invention has the purpose of simultaneously solving these problems, and is therefore particularly suitable for use in a liquid phase.
As the liquid phase, any portion other than the granulated adsorbent can be used without any problem as long as it is a uniform liquid phase.For example, an organic solvent solution can also be used. It is preferably used in an aqueous solution for the purpose of recovery of useful substances, recovery of useful substances, and the like.
一方、バインダーはポリオレフィン系樹脂であってもよい。樹脂には、吸着材の表面を覆う恐れがあるものもあるが、ポリオレフィン系樹脂は、樹脂が疎水性であるため、このような恐れがない。また造粒吸着材の製造が容易である点から、ポリオレフィン系樹脂は、エマルジョン形態であることが好ましい。
ポリオレフィン系樹脂としてとしては、ポリエチレン（直鎖状低密度ポリエチレン等の低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン等）、ポリプロピレン、エチレン−プロピレン共重合体、エチレン又はプロピレンと他のα−オレフィンとの共重合体、さらにエチレン又はプロピレンと（メタ）アクリル酸、（メタ）アクリル酸エステル、酢酸ビニル、ビニルアルコール、スチレン等の不飽和単量体との共重合体等が例示される。On the other hand, the binder may be a polyolefin-based resin. Some resins may cover the surface of the adsorbent, but polyolefin-based resins do not have such a risk because the resin is hydrophobic. The polyolefin-based resin is preferably in the form of an emulsion in that the production of the granulated adsorbent is easy.
Examples of the polyolefin resin include polyethylene (low-density polyethylene such as linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, etc.), polypropylene, ethylene-propylene copolymer, ethylene or propylene and other α-olefins. And copolymers of ethylene or propylene with unsaturated monomers such as (meth) acrylic acid, (meth) acrylic acid ester, vinyl acetate, vinyl alcohol, and styrene.
（吸着速度）
本発明の吸着材粒子及び造粒吸着材は、吸着速度が高い特徴を有する。
この吸着速度は、次のような回分式吸着試験により測定できる。
塩酸でｐＨを一定に調整したリン換算濃度４００ｍｇ／Ｌのリン酸二水素カリウム水溶液１５０ｍＬを準備する。この中に吸着材１ｇを投入し、室温で撹拌する。一定時間後に水溶液をサンプリングしてリン酸イオン濃度を測定し、吸着量を求める。
また以上の試験において、経時的にリン酸イオン吸着量を求め、経時変化がなくなった時点での吸着量により、最終的吸着量を見積もることができる。より簡便には、２４時間後の吸着量により最終的吸着量を見積もることができる。
本発明の吸着材粒子及び造粒吸着材は、この方法において、水溶液のｐＨを３．５に調整した場合、２４時間後にリン換算吸着量が２２ｍｇ以上、より好ましくは３０ｍｇ以上となる。(Suction speed)
The adsorbent particles and the granulated adsorbent of the present invention have a feature that the adsorption speed is high.
This adsorption rate can be measured by the following batch adsorption test.
A 150 mL aqueous solution of potassium dihydrogen phosphate having a concentration of 400 mg / L in terms of phosphorus, which is adjusted to a constant pH with hydrochloric acid, is prepared. Into this, 1 g of the adsorbent is put and stirred at room temperature. After a certain period of time, the aqueous solution is sampled, the phosphate ion concentration is measured, and the adsorption amount is determined.
In the above test, the amount of adsorbed phosphate ions is determined over time, and the final amount of adsorption can be estimated from the amount of adsorption at the time when there is no change with time. More simply, the final adsorption amount can be estimated from the adsorption amount after 24 hours.
When the pH of the aqueous solution of the adsorbent particles and the granulated adsorbent of the present invention is adjusted to 3.5 in this method, the adsorption amount in terms of phosphorus becomes 22 mg or more, more preferably 30 mg or more after 24 hours.
また本発明の吸着材粒子及び造粒吸着材は、水中で陰イオン吸着材として使用する過程で、ｐＨが顕著に上昇することを特徴とする。これは、具体的には次の方法で示される。
塩酸でｐＨを一定に調整したリン換算濃度４００ｍｇ／Ｌのリン酸二水素カリウム水溶液１５０ｍＬを準備する。この中に吸着材１ｇを投入し、室温で撹拌する。一定時間後に水溶液をサンプリングしてｐＨを測定する。
本発明の吸着材粒子及び造粒吸着材は、この方法において、水溶液のｐＨを３．５に調整した場合、１時間後の水溶液のｐＨに対して２４時間後の水溶液のｐＨが０．５以上上昇する。
ところが、本発明の吸着材粒子の材料として用いられるβ−オキシ水酸化鉄は、粒子径がある程度微小でないと、吸着材として使用してもほとんど水溶液のｐＨの変化をもたらさない。Further, the adsorbent particles and the granulated adsorbent of the present invention are characterized in that the pH is significantly increased in the process of using the adsorbent particles in water as an anion adsorbent. This is specifically shown by the following method.
A 150 mL aqueous solution of potassium dihydrogen phosphate having a concentration of 400 mg / L in terms of phosphorus, which is adjusted to a constant pH with hydrochloric acid, is prepared. Into this, 1 g of the adsorbent is put and stirred at room temperature. After a certain period of time, the aqueous solution is sampled to measure the pH.
In this method, when the pH of the aqueous solution is adjusted to 3.5 in this method, the pH of the aqueous solution after 24 hours is 0.5 to the pH of the aqueous solution after 1 hour. Or more.
However, β-iron oxyhydroxide used as a material of the adsorbent particles of the present invention hardly causes a change in pH of an aqueous solution even when used as an adsorbent, unless the particle diameter is small to some extent.
これらの原因は、次のように推察される。粉砕等の処理をしていないβ−オキシ水酸化鉄では、水酸基がリン酸イオンのような大きな陰イオンの容易に到達し得ない細孔中にある。このような細孔は、特に塩素イオンが離脱することにより形成されるものである。一方、本発明の吸着材は、このような細孔構造が破壊されているため、リン酸イオンも容易に該水酸基の近傍に到達する。
粒度の調整をしていないβ−オキシ水酸化鉄でも、大型の空孔があるため、吸着速度は遅いもののリン酸イオンの吸着は可能である。
本発明の吸着材においては、これに続き、吸着された陰イオンが水酸基と置換し、吸着材に該陰イオンが直接結合した形に変化し、それとともに、水酸基は水酸イオンとして水中に放出されるため、水溶液のｐＨは上昇する。しかし粉砕等の処理をしていないβ−オキシ水酸化鉄では、このような置換は起こらず、従ってｐＨの上昇も起こらないものと推察される。
以上により、本発明の吸着材は、陰イオンを単に吸着するのみでなく、その後陰イオンは吸着材に結合して容易に解離しない状態となるため、高い吸着効率を発揮するものと考えられる。These causes are presumed as follows. In β-iron oxyhydroxide that has not been subjected to a treatment such as pulverization, the hydroxyl groups are in pores where large anions such as phosphate ions cannot easily reach. Such pores are formed particularly when chlorine ions are released. On the other hand, in the adsorbent of the present invention, since such a pore structure is destroyed, phosphate ions easily reach the vicinity of the hydroxyl group.
Even for β-iron oxyhydroxide without adjusting the particle size, phosphate ions can be adsorbed although the adsorption speed is slow because of the presence of large pores.
In the adsorbent of the present invention, subsequently, the adsorbed anion replaces the hydroxyl group and changes to a form in which the anion is directly bonded to the adsorbent, and the hydroxyl group is released into water as hydroxyl ion. Therefore, the pH of the aqueous solution rises. However, in β-iron oxyhydroxide that has not been subjected to a treatment such as pulverization, such substitution does not occur, and thus it is presumed that the pH does not increase.
From the above, it is considered that the adsorbent of the present invention not only simply adsorbs anions, but also thereafter binds to the adsorbent and is not easily dissociated, thereby exhibiting high adsorption efficiency.
本発明の吸着材は、陰イオン吸着後に、水中で塩基と接触させてアルカリ性とすることにより、該陰イオンを脱着させることができる。
従来、リン酸イオン等の陰イオンの回収法としては、水難溶性の化合物として回収する方法が多く用いられており、この方法は単に回収する場合には適していたが、回収物を再利用するための処理に手間がかかっていた。しかし本発明の吸着材を用いれば、水溶性の塩の高濃度水溶液として回収することが可能であり、その後の処理も容易である。
前記の脱着に用いる塩基としては、特に限定されないが、上記の処理の容易さから、脱着処理により生成する塩の水溶解度が高いものである方が好ましく、また陰イオンの種類や後処理方法に応じて選択することができる。例示すれば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩、アンモニア等を使用することができる。
これらの塩基を水溶液とし、陰イオンを吸着させた本発明の吸着材と接触させることにより、該陰イオンを脱着させ水溶液中に溶出させることができる。この水溶液のｐＨとしては、１０以上であることが好ましく、１３以上であることが特に好ましい。The adsorbent of the present invention can desorb the anion by contacting the base with the base in water to make it alkaline after the adsorption of the anion.
Conventionally, as a method for recovering anions such as phosphate ions, a method of recovering as a poorly water-soluble compound has been widely used, and this method was suitable for simply recovering, but the recovered material was reused. It took time to process. However, if the adsorbent of the present invention is used, it can be recovered as a high-concentration aqueous solution of a water-soluble salt, and the subsequent treatment is also easy.
The base used for the desorption is not particularly limited, but is preferably one having a high water solubility of a salt generated by the desorption treatment from the easiness of the above treatment, and depending on the type of anion and the post-treatment method. Can be selected accordingly. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, ammonia and the like can be used.
By making these bases into an aqueous solution and bringing them into contact with the adsorbent of the present invention having anions adsorbed thereon, the anions can be desorbed and eluted in the aqueous solution. The pH of the aqueous solution is preferably 10 or more, and particularly preferably 13 or more.
本発明の吸着材粒子又は造粒吸着材は、通水性を有し、該吸着材粒子又は造粒吸着材を通さない容器に収納して、使用することもできる。これにより、吸着材の回収、吸着物質の脱着、及び吸着の反復使用が容易になる。
この通水性を有し吸着材粒子又は造粒吸着材を通さない容器としては、孔径が吸着材粒子粒径又は造粒吸着材より小さい細孔、好ましくは１０μｍ以下、より好ましくは５μｍ以下である細孔を多数有する容器を用いることができる。具体的には細孔を有するセラミック、合成樹脂等からなる容器、不織布からなる袋、また通水孔部分を不織布で覆った容器等が挙げられる。The adsorbent particles or granulated adsorbent of the present invention has water permeability and can be used by being housed in a container through which the adsorbent particles or granulated adsorbent does not pass. This facilitates the repeated use of the recovery of the adsorbent, the desorption of the adsorbed substance, and the adsorption.
As a container having this water permeability and not allowing the adsorbent particles or the granulated adsorbent to pass through, the pore diameter is smaller than the adsorbent particle diameter or the granulated adsorbent, preferably 10 μm or less, more preferably 5 μm or less. A container having many pores can be used. Specific examples include a container made of ceramic or synthetic resin having pores, a bag made of a nonwoven fabric, a container having a water passage hole covered with a nonwoven fabric, and the like.
次に、本発明の実施例によってさらに詳細に説明するが、本発明はこれにより限定されるものではない。 Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
測定方法
（粉末Ｘ線回折）
Ｘ線回折（ＸＲＤ）パターンは、Ｘ線回折装置Ultima ＩＶ（リガク社製）を用いて測定した。測定にはＣｕＫα管球を使用した。平均結晶子径はＸＲＤよりシェラーの式に従って算出した。
（比表面積）
比表面積測定装置MacsorbHM 1210（マウンテック社製）を使用して、ガス吸着法により比表面積を測定した。
（ＴＥＭ観察及びＦＦＴ解析）
試料のＴＥＭ（透過電子顕微鏡）観察は、透過型電子顕微鏡ＪＥＭ ２０１０Ｆ（ＪＥＯＬ社製、加速電圧２００ｋＶ）を用いて行った。またこれによるＦＦＴ（高速フーリエ変換）解析は、Ｇａｔａｎ社製Ｄｉｇｉｔａｌ Ｍｉｃｒｏｇｒａｐｈを用いて行なった。
（オキシ水酸化鉄中の塩素イオンの含有量）
オキシ水酸化鉄試料を３Ｍ硫酸に溶解した後、アルカリ溶液で希釈して鉄分を沈殿させ、フィルターでろ過してろ液を回収し、イオンクロマトグラフ法（日本ダイオネクス社製DX-500型）により定量した。
（分散液の粘度）
２０℃で、音叉型振動式粘度計ＳＶ−１０（エー・アンド・デイ社製）により測定した。
（分散液の粒度分布）
ミクロン単位の分散液の粒子径に関しては、レーザ回折／散乱式粒度分布測定装置LA-920（堀場製作所製）を使用して、体積基準の累積５０％粒子径（Ｄ５０）、及び体積基準の累積９０％粒子径（Ｄ９０）を測定した。
ナノ分散液の粒子径、粒度分布、累積５０％粒子径（Ｄ５０）、及び累積９０％粒子径（Ｄ９０）は、動的光散乱粒度分布測定装置ゼータサイザーナノＳ（スペクトリス社製）を使用して測定した。
（分散粒子のゼータ電位）
ゼータ電位は、ナノトラック（Nanotrac Wave ＵＺ152、日機装社製）を用いて測定した。Measurement method (powder X-ray diffraction)
The X-ray diffraction (XRD) pattern was measured using an X-ray diffractometer Ultima IV (manufactured by Rigaku Corporation). A CuKα bulb was used for the measurement. The average crystallite diameter was calculated from XRD according to Scherrer's formula.
(Specific surface area)
The specific surface area was measured by a gas adsorption method using a specific surface area measuring device MacsorbHM 1210 (manufactured by Mountech).
(TEM observation and FFT analysis)
The sample was observed with a transmission electron microscope (TEM) using a transmission electron microscope JEM 2010F (manufactured by JEOL, accelerating voltage 200 kV). The FFT (Fast Fourier Transform) analysis was performed using a Digital Micrograph manufactured by Gatan.
(Content of chlorine ion in iron oxyhydroxide)
After dissolving the iron oxyhydroxide sample in 3M sulfuric acid, dilute it with an alkaline solution to precipitate the iron content, collect the filtrate by filtration with a filter, and quantify it by ion chromatography (DX-500, manufactured by Nippon Dionex). did.
(Viscosity of dispersion liquid)
The viscosity was measured at 20 ° C. with a tuning fork vibrating viscometer SV-10 (manufactured by A & D).
(Particle size distribution of dispersion)
Regarding the particle diameter of the dispersion liquid in micron units, the laser diffraction / scattering type particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) was used to calculate the volume-based cumulative 50% particle diameter (D50) and the volume-based cumulative The 90% particle size (D90) was measured.
The particle size, particle size distribution, cumulative 50% particle size (D50), and cumulative 90% particle size (D90) of the nanodispersion were measured using a dynamic light scattering particle size distribution analyzer, Zetasizer Nano S (manufactured by Spectris). Measured.
(Zeta potential of dispersed particles)
The zeta potential was measured using Nanotrac (Nanotrac Wave UZ152, manufactured by Nikkiso Co., Ltd.).
参考例１（オキシ水酸化鉄の製造）
塩化第二鉄（ＦｅＣｌ３）水溶液に、室温でｐＨ６以下に調整しながら水酸化ナトリウム（ＮａＯＨ）水溶液を滴下し、ＮａＯＨの最終添加量をＮａＯＨ／ＦｅＣｌ３（モル比）＝２．７５として反応させ、オキシ水酸化鉄の粒子懸濁液を得た。得られた懸濁液中の粒子の平均粒子径ｄ５０は１７μｍであった。
懸濁液を濾別後、空気中１２０℃で乾燥し、イオン交換水で洗浄し、さらに空気中１２０℃で乾燥し、オキシ水酸化鉄の粉末を得た。
以上により得られたオキシ水酸化物粉末（粉末Ａ）の粒子径は０．２５ｍｍ〜５ｍｍであった。Ｘ線回折により、結晶構造はβ−オキシ水酸化鉄であり、平均結晶子径は５ｎｍであることを確認した。
透過電子顕微鏡（ＴＥＭ）観察での様子を図１に示す。結晶形状は粒状であった。ＴＥＭ観察による結晶子径は５〜１０ｎｍ、個々の結晶は粒状であり、これらが凝結して粒子を形成していた。
また比表面積は２８０ｍ２／ｇ、塩素イオン含有量は、５．８ｗｔ％であった。Reference Example 1 (production of iron oxyhydroxide)
An aqueous solution of sodium hydroxide (NaOH) was added dropwise to an aqueous solution of ferric chloride (FeCl 3 ) while adjusting the pH to 6 or less at room temperature, and the reaction was performed with the final addition amount of NaOH being NaOH / FeCl 3 (molar ratio) = 2.75. Then, a particle suspension of iron oxyhydroxide was obtained. The average particle diameter d50 of the particles in the obtained suspension was 17 μm.
After the suspension was separated by filtration, the suspension was dried at 120 ° C. in air, washed with ion-exchanged water, and further dried at 120 ° C. in air to obtain iron oxyhydroxide powder.
The particle diameter of the oxyhydroxide powder (powder A) obtained as described above was 0.25 mm to 5 mm. X-ray diffraction confirmed that the crystal structure was β-iron oxyhydroxide and the average crystallite size was 5 nm.
FIG. 1 shows a state observed by a transmission electron microscope (TEM). The crystal shape was granular. The crystallite diameter by TEM observation was 5 to 10 nm, and the individual crystals were granular, and these were coagulated to form particles.
The specific surface area was 280 m 2 / g, and the chloride ion content was 5.8 wt%.
参考例２（オキシ水酸化鉄吸着材粒子の製造）
オキシ水酸化鉄粉末（粉末Ａ）をピンミルで乾式粉砕し、図２に示す粒度分布の粉末（粉末Ｂ）を得た。粉末Ｂの粒子径範囲は０．６〜３００μｍ、平均粒子径２６．５μｍであった。Reference Example 2 (Production of iron oxyhydroxide adsorbent particles)
The iron oxyhydroxide powder (powder A) was dry-pulverized with a pin mill to obtain a powder (powder B) having a particle size distribution shown in FIG. The particle size range of the powder B was 0.6 to 300 µm, and the average particle size was 26.5 µm.
実施例１〜３（オキシ水酸化鉄吸着材分級品）
粉末Ｂを篩で分級し、以下の各粉末を得た。
粉末Ｃ−１：粒度１０〜３２μｍ
粉末Ｃ−２：粒度３２〜４５μｍ
粉末Ｃ−３：粒度４５〜７５μｍExamples 1 to 3 (classified product of iron oxyhydroxide adsorbent)
Powder B was classified with a sieve to obtain the following powders.
Powder C-1: Particle size 10 to 32 μm
Powder C-2: Particle size 32-45 μm
Powder C-3: Particle size of 45 to 75 μm
比較例１
粉末Ｂを篩で分級し、粒度１５０〜２５０μｍの粉末Ｃ−４を得た。Comparative Example 1
Powder B was classified with a sieve to obtain powder C-4 having a particle size of 150 to 250 µm.
実施例４（１０μｍアンダーを回収した粒子の製造）
粉末Ｂを篩目１０μｍのナイロンメッシュで包み、イオン交換水に入れ、十分に洗浄して粒径１０μｍ以下を回収し、粒子径範囲８〜３００μｍ、平均粒子径４０．３μｍの粉末（粉末Ｄ）を得た。
以上の粉末Ｂ、粉末Ｄ（メッシュ残存物）及びメッシュ通過品（上記の除去分）の粒径分布を図２に示した。Example 4 (Production of particles recovered from under 10 μm)
The powder B is wrapped with a 10 μm mesh nylon mesh, put in ion-exchanged water, and sufficiently washed to collect a particle diameter of 10 μm or less. A powder having a particle diameter range of 8 to 300 μm and an average particle diameter of 40.3 μm (powder D) I got
FIG. 2 shows the particle size distribution of the powder B, powder D (mesh residue) and the product having passed through the mesh (the above-mentioned removed portion).
参考例３（オキシ水酸化鉄のナノ分散液の製造）
粉末Ｂをイオン交換水中に固形分濃度１０質量％となるように混合した後、ビーズミル（ジルコニアビーズ、ビーズ径１ｍｍ）で３０分間粗粉砕し懸濁液とした。これをさらに、ビーズミル（ジルコニアビーズ、ビーズ径０．１ｍｍ）で６０分間粉砕し、分散液Ｅを得た。この粉砕により、茶色に懸濁していた液が黒色で透明なナノ分散液Ｅへ変化した。
ナノ分散液ＥのｐＨは３．１、平均粒子径ｄ５０は０．１５μｍ、ｄ９０は０．２７μｍ、等電点はｐＨ７．１であった。
また本分散液Ｅを５０℃で乾燥した粉末の結晶構造はβ−オキシ水酸化鉄、結晶子径は２ｎｍで、比表面積は２８５ｍ２／ｇであった。Reference Example 3 (Production of nanodispersion of iron oxyhydroxide)
Powder B was mixed in ion-exchanged water so as to have a solid concentration of 10% by mass, and then roughly pulverized for 30 minutes using a bead mill (zirconia beads, bead diameter 1 mm) to form a suspension. This was further pulverized by a bead mill (zirconia beads, bead diameter: 0.1 mm) for 60 minutes to obtain a dispersion E. By this pulverization, the liquid suspended in brown was changed to a black and transparent nano-dispersion E.
The nanodispersion E had a pH of 3.1, an average particle diameter d50 of 0.15 μm, a d90 of 0.27 μm, and an isoelectric point of pH 7.1.
The crystal structure of the powder obtained by drying the dispersion E at 50 ° C. was β-iron oxyhydroxide, the crystallite diameter was 2 nm, and the specific surface area was 285 m 2 / g.
実施例５〜７（造粒品の製造）
吸着材である粉末Ｄと、以下に示す各種バインダーとを所定の質量比で混合した後、１２０℃で乾燥し、更に篩で０．２５ｍｍ〜０．５ｍｍの大きさに整粒し、造粒品群（造粒品Ｆ１〜Ｆ３）を調製した。
＜バインダーの種類及び比率＞
吸着材としては粉末Ｄを、バインダーとしては下記の各分散液を使用し、これらを下記の質量比として造粒品を得た。
・造粒品Ｆ１： 前記分散液Ｅ（吸着材：バインダー＝９：１）
・造粒品Ｆ２： 前記分散液Ｅ（吸着材：バインダー＝８：２）
・造粒品Ｆ３： ジルコニアナノ分散液（分散液Ｅ２、粒径６０〜１００ｎｍ、ｐＨ７．０〜８．０、固形分濃度１０質量％）（吸着材：バインダー＝９：１）Examples 5 to 7 (production of granulated product)
After mixing powder D as an adsorbent and various binders shown below at a predetermined mass ratio, the mixture is dried at 120 ° C., and further sized with a sieve to a size of 0.25 mm to 0.5 mm, and granulated. Product groups (granulated products F1 to F3) were prepared.
<Type and ratio of binder>
Powder D was used as the adsorbent, and the following dispersions were used as the binder. Granules were obtained with the following mass ratios.
-Granulated product F1: The dispersion E (adsorbent: binder = 9: 1)
-Granulated product F2: Dispersion E (adsorbent: binder = 8: 2)
-Granulated product F3: zirconia nano dispersion (dispersion E2, particle size 60 to 100 nm, pH 7.0 to 8.0, solid content concentration 10 mass%) (adsorbent: binder = 9: 1)
測定例１（吸着材粒子のリン酸吸着試験）
リン酸二水素カリウムをイオン交換水に溶解し、塩酸によりｐＨを３．５に調整し、濃度４００ｍｇ−Ｐ／Ｌ（リンとしての濃度）の試験液Ｇを調製した。試験液Ｇの１５０ｍＬに、粉末Ａ、Ｂ、Ｃ−１〜５、Ｄ〜Ｆの各１ｇを添加後、撹拌し吸着試験を行った。所定の時間後に液を採取し、フィルタシリンジで固形分と分離し、溶液中のリン濃度をＩＣＰ（誘導結合プラズマ）により分析し、吸着量を算出した。同時にｐＨを測定した。結果を表１及び表２に示した。Measurement example 1 (phosphoric acid adsorption test of adsorbent particles)
Potassium dihydrogen phosphate was dissolved in ion-exchanged water, the pH was adjusted to 3.5 with hydrochloric acid, and a test solution G having a concentration of 400 mg-P / L (concentration as phosphorus) was prepared. After adding 1 g of each of powders A, B, C-1 to 5, and D to F to 150 mL of test solution G, the mixture was stirred and an adsorption test was performed. After a predetermined time, the liquid was collected, separated from the solid content with a filter syringe, and the phosphorus concentration in the solution was analyzed by ICP (inductively coupled plasma) to calculate the amount of adsorption. At the same time, the pH was measured. The results are shown in Tables 1 and 2.
以上からわかるように、平均粒径ｄ５０を１０〜７０μｍとした分級品は、２４時間後のｐＨが４以上となった。また、造粒品も含めて、２４時間後のｐＨが４以上となる吸着材粉末は、吸着速度が顕著に高く、１時間後の吸着量が２２ｍｇ−Ｐ／ｇ以上であった。
As can be seen from the above, the classified product having an average particle size d50 of 10 to 70 μm had a pH of 4 or more after 24 hours. In addition, the adsorbent powder having a pH of 4 or more after 24 hours, including the granulated product, had a remarkably high adsorption rate, and the adsorption amount after 1 hour was 22 mg-P / g or more.
測定例２（メッシュ袋入り吸着材粒子のリン酸吸着試験）
実施例４で得られた吸着材粒子（粉末Ｄ）を使用した。袋状の目開き１０μｍのナイロンメッシュに粉末Ｄ１．０ｇを入れ、袋口をヒートシールにて封をした。
測定例１と同様に試験液Ｇを調製した。試験液Ｇの１５０ｍＬに、上記吸着材入りメッシュ袋１個を入れ撹拌し、測定例１と同様に吸着試験を行った。所定の時間後に液を採取し、溶液中のリン濃度をＩＣＰ（誘導結合プラズマ）により分析し、吸着量を算出した。同時にｐＨを測定した。結果を表３に示した。Measurement Example 2 (Phosphoric acid adsorption test of adsorbent particles in mesh bag)
The adsorbent particles (powder D) obtained in Example 4 were used. 1.0 g of powder D was placed in a bag-shaped nylon mesh having an opening of 10 μm, and the bag mouth was sealed by heat sealing.
Test liquid G was prepared in the same manner as in Measurement Example 1. One mesh bag containing the adsorbent was placed in 150 mL of the test solution G and stirred, and an adsorption test was performed in the same manner as in Measurement Example 1. After a predetermined time, the solution was collected, and the phosphorus concentration in the solution was analyzed by ICP (inductively coupled plasma) to calculate the amount of adsorption. At the same time, the pH was measured. The results are shown in Table 3.
以上のように、メッシュ袋入り吸着材を用いても、吸着時間２４時間では測定例１と同程度の吸着量を示し、ｐＨの上昇も見られた。 As described above, even when the adsorbent contained in the mesh bag was used, the adsorption amount was approximately the same as that in Measurement Example 1 at an adsorption time of 24 hours, and an increase in pH was also observed.
実施例８（塩素イオン含有量調整品）
参考例２（粉末Ｂ）と同様にして得られたオキシ水酸化鉄吸着材粒子を、篩で分級し、粒子径範囲１０〜２００μｍ、平均粒子径４９．９μｍの粉末（粉末Ｃ’）を得た。
粉末Ｃ’をカラムに詰め、１０ｗｔ％水酸化ナトリウム水溶液を通液した後、ｐＨ２．５の希塩酸を通液し、粉末Ｃ−５を得た。Example 8 (chlorine ion content adjusted product)
The iron oxyhydroxide adsorbent particles obtained in the same manner as in Reference Example 2 (powder B) are classified with a sieve to obtain a powder (powder C ′) having a particle diameter range of 10 to 200 μm and an average particle diameter of 49.9 μm. Was.
The powder C ′ was packed in a column, and after passing a 10 wt% aqueous sodium hydroxide solution, dilute hydrochloric acid having a pH of 2.5 was passed to obtain Powder C-5.
実施例９（塩素イオン含有量調整品）
実施例８と同様に粉末Ｃ’をカラムに詰めて１０ｗｔ％水酸化ナトリウム水溶液及びｐＨ２．５希塩酸の通液を行った。さらにこれに純水を通液し、流出液に塩素が含まれなくなるまで純水の通液を行い、粉末Ｃ−６を得た。
粉末Ｃ−５及びＣ−６の比表面積、全細孔容量、平均結晶子径、及び塩素イオン含有量を測定した結果を表４に示した。Example 9 (Chloride ion content adjusted product)
In the same manner as in Example 8, the powder C ′ was packed in a column, and a 10 wt% aqueous sodium hydroxide solution and pH 2.5 diluted hydrochloric acid were passed through the column. Further, pure water was passed through this, and pure water was passed until the effluent contained no chlorine, thereby obtaining powder C-6.
Table 4 shows the measurement results of the specific surface area, the total pore volume, the average crystallite diameter, and the chloride ion content of the powders C-5 and C-6.
測定例３（塩素イオン含有量調整品のリン酸吸着試験）
測定例１と同様にして、試験液Ｇ１５０ｍＬに、粉末Ｃ−５及びＣ−６の各１ｇを添加後、撹拌し吸着試験を行い、リン酸吸着量及びｐＨの変化を測定した。結果を表５に示した。Measurement Example 3 (Phosphoric acid adsorption test of chlorine ion content adjusted product)
In the same manner as in Measurement Example 1, 1 g of each of the powders C-5 and C-6 was added to 150 mL of the test solution G, followed by stirring to conduct an adsorption test, and the change in the amount of adsorbed phosphoric acid and the change in pH were measured. Table 5 shows the results.
以上から、塩素イオン含有量が高い方（特に３ｗｔ％程度以上）が吸着量及び吸着速度に関して好ましいことがわかる。またこの特長は比表面積等の構造的要因によるものではないことが示唆される。 From the above, it can be seen that a higher chloride ion content (especially about 3 wt% or more) is preferable with respect to the adsorption amount and the adsorption rate. It is also suggested that this feature is not due to structural factors such as specific surface area.
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