JP6252143B2 - Recycling method of boron adsorbent - Google Patents
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- 239000003463 adsorbent Substances 0.000 title claims description 131
- 229910052796 boron Inorganic materials 0.000 title claims description 95
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims description 93
- 238000000034 method Methods 0.000 title claims description 38
- 238000004064 recycling Methods 0.000 title claims description 18
- 239000002002 slurry Substances 0.000 claims description 55
- 238000004140 cleaning Methods 0.000 claims description 36
- 239000002952 polymeric resin Substances 0.000 claims description 36
- 229920003002 synthetic resin Polymers 0.000 claims description 35
- 239000003513 alkali Substances 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 17
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000008187 granular material Substances 0.000 description 20
- 238000001179 sorption measurement Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- HGVAXMJKHJAZGW-UHFFFAOYSA-N CC=C.F.F.F.F.F.F.F Chemical group CC=C.F.F.F.F.F.F.F HGVAXMJKHJAZGW-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Description
本発明は、高分子樹脂が劣化したホウ素吸着剤を有効に再利用するリサイクル方法に関する。 The present invention relates to a recycling method for effectively reusing a boron adsorbent having a deteriorated polymer resin.
ホウ素化合物は、医薬品、化粧品、石けん、電気メッキなどの種々の用途に使用されるため、これらの製造工程などから発生する排水にはホウ素が含まれている。また、石炭焚き火力発電所の脱硫排水やごみ焼却場の洗煙排水等にもホウ素が含まれている場合がある。 Boron compounds are used in various applications such as pharmaceuticals, cosmetics, soaps, and electroplating, so that wastewater generated from these manufacturing processes contains boron. Also, desulfurization effluent from coal-fired thermal power plants and smoke effluent from a garbage incineration plant may contain boron.
このようなホウ素含有排水の処理方法として、ホウ素吸着剤にホウ素を吸着させて除去する方法が知られており、この方法で使用されるホウ素吸着剤として、高分子樹脂と希土類元素水酸化物との混合物よりなるものが提案されている（特許文献１）。
このホウ素吸着剤は、高分子樹脂１００重量部当たり、ホウ素吸着成分である希土類元素水酸化物６００重量部以上を含むものである。
As a method for treating such boron-containing wastewater, a method for removing boron by adsorbing boron to a boron adsorbent is known. As a boron adsorbent used in this method, a polymer resin and a rare earth element hydroxide are used. The thing which consists of a mixture of these is proposed (patent document 1).
This boron adsorbent contains 600 parts by weight or more of rare earth element hydroxide as a boron adsorbing component per 100 parts by weight of the polymer resin.
上記のホウ素吸着剤による処理は、通常、ホウ素吸着剤を充填したカラムにホウ素含有排水を通液するホウ素吸着工程と、その後、アルカリを通液してホウ素吸着剤に吸着されたホウ素を脱着させてホウ素吸着剤を再生する再生工程とを繰り返すことにより行われるが、処理時間が長く、処理排水量が多くなり、ホウ素吸着剤がこの吸着工程と再生工程を繰り返し受けることにより、ホウ素吸着剤を構成する高分子樹脂が劣化し、微細化ないしは収縮を起こす。 The above treatment with a boron adsorbent usually involves a boron adsorption step in which boron-containing wastewater is passed through a column filled with boron adsorbent, and then an alkali is passed through to desorb boron adsorbed on the boron adsorbent. This process is performed by repeating the regeneration process for regenerating the boron adsorbent, but the treatment time is long and the amount of treated wastewater increases, and the boron adsorbent is configured by repeating this adsorption process and the regeneration process. The polymer resin to be deteriorated, causing fineness or shrinkage.
このように高分子樹脂が劣化して微細化ないしは収縮したホウ素吸着剤（以下「劣化吸着剤」と称す場合がある。）は、処理時の通液差圧上昇の原因となるため、従来、劣化吸着剤は、カラムから漉き取り、廃棄処分されていた。 The boron adsorbent (hereinafter sometimes referred to as “deteriorated adsorbent”), which has been degraded or refined due to degradation of the polymer resin in this way, causes an increase in the differential pressure during processing. The deteriorated adsorbent was scraped from the column and discarded.
本発明は、このように、従来、廃棄されている劣化吸着剤を回収して有効に再利用するホウ素吸着剤のリサイクル方法を提供することを目的とする。 Thus, the present invention has an object to provide a method for recycling a boron adsorbent that recovers and effectively reuses a previously deteriorated adsorbent.
使用により劣化したホウ素吸着剤は、主として高分子樹脂が劣化することにより微細化ないしは収縮したものであり、ホウ素吸着成分である希土類元素水酸化物については殆ど劣化していない。
本発明者らは、この劣化していない希土類元素水酸化物を有効再利用するべく鋭意検討を重ねた結果、劣化吸着剤を有機溶媒に溶解させて所定の粘度のスラリーとし、これを造粒することで、ホウ素吸着剤として再利用可能な形態に復元することができること、更には、有機溶媒への溶解に先立ち薬品による洗浄を行うことで、スラリー粘度の調整を容易とすると共に、ホウ素吸着性能を回復させて再生することができることを見出した。
The boron adsorbent deteriorated by use is refined or contracted mainly due to deterioration of the polymer resin, and rare earth element hydroxide which is a boron adsorbing component is hardly deteriorated.
As a result of intensive studies to effectively recycle the non-degraded rare earth element hydroxide, the present inventors dissolved the degraded adsorbent in an organic solvent to form a slurry having a predetermined viscosity, and granulated this. As a result, it can be restored to a form that can be reused as a boron adsorbent, and furthermore, by washing with chemicals prior to dissolution in an organic solvent, the slurry viscosity can be easily adjusted and boron adsorption can be achieved. It has been found that performance can be recovered and played back.
本発明はこのような知見に基づいて達成されたものであり、以下を要旨とする。 The present invention has been achieved based on such findings, and the gist thereof is as follows.
［１］ バインダーとしての高分子樹脂と、ホウ素吸着成分である希土類元素水酸化物との混合物よりなるホウ素吸着剤中に含まれる該高分子樹脂が劣化したホウ素吸着剤をリサイクルする方法であって、該高分子樹脂が劣化したホウ素吸着剤を有機溶媒と混合して該ホウ素吸着剤中の高分子樹脂が溶解したスラリーを得る溶解工程と、該溶解工程で得られたスラリーを造粒する造粒工程とを有し、該造粒工程に供するスラリーの５０℃換算の粘度が２００〜１６００ｃＰであることを特徴とするホウ素吸着剤のリサイクル方法。 [1] and the polymer resin as a binder, a method for recycling boron adsorbent wherein the polymer resin has degraded contained boron in the adsorbent comprising a mixture of a rare earth element hydroxide is boron adsorbed component , granulated for granulating a melting step of obtaining a slurry polymer resin is dissolved in the boron adsorbent is mixed with an organic solvent a boron adsorbent wherein the polymer resin is deteriorated, the slurry obtained in the dissolution step A method for recycling a boron adsorbent, wherein the slurry used in the granulation step has a viscosity in terms of 50 ° C. of 200 to 1600 cP.
［２］ ［１］において、前記溶解工程で得られたスラリーに新品のホウ素吸着剤を添加することにより該スラリーの５０℃換算の粘度を２００〜１６００ｃＰに調整することを特徴とするホウ素吸着剤のリサイクル方法。 [2] In [1], a new boron adsorbent is added to the slurry obtained in the dissolving step to adjust the viscosity of the slurry to 50 ° C. to 200 to 1600 cP. Recycling method.
［３］ ［１］又は［２］において、前記溶解工程に先立ち、前記劣化したホウ素吸着剤を酸及び／又はアルカリで洗浄する洗浄工程を有することを特徴とするホウ素吸着剤のリサイクル方法。 [3] A method for recycling a boron adsorbent according to [1] or [2], further comprising a cleaning step of cleaning the deteriorated boron adsorbent with an acid and / or alkali prior to the dissolving step.
［４］ ［３］において、前記洗浄工程において、前記劣化したホウ素吸着剤をカラムに充填し、該カラムに０．５Ｎ以上の酸を２ＢＶ以上通液する酸洗浄と、０．５Ｎ以上のアルカリを２ＢＶ以上通液するアルカリ洗浄のいずれか一方又は双方を行うことを特徴とするホウ素吸着剤のリサイクル方法。 [4] In [3], in the cleaning step, the deteriorated boron adsorbent is packed in a column, an acid cleaning in which 0.5 N or more acid is passed through the column through 2 BV or more, and an alkali of 0.5 N or more. A method for recycling a boron adsorbent characterized by performing either one or both of alkali cleaning for passing 2 BV or more.
［５］ ［３］又は［４］において、前記洗浄工程で洗浄したホウ素吸着剤を、６５℃未満の温度で乾燥させる乾燥工程を有し、該乾燥工程後のホウ素吸着剤が前記溶解工程に供されることを特徴とするホウ素吸着剤のリサイクル方法。 [5] In [3] or [4], the method includes a drying step of drying the boron adsorbent washed in the washing step at a temperature of less than 65 ° C., and the boron adsorbent after the drying step is included in the dissolving step. A method for recycling a boron adsorbent characterized by being provided.
［６］ ［１］ないし［５］のいずれかにおいて、前記ホウ素吸着剤が高分子樹脂と希土類元素水酸化物とを含むことを特徴とするホウ素吸着剤のリサイクル方法。 [6] The method for recycling a boron adsorbent according to any one of [1] to [5], wherein the boron adsorbent includes a polymer resin and a rare earth element hydroxide.
本発明によれば、長期使用により劣化したホウ素吸着剤を、有機溶媒に溶解させて得られたスラリーを造粒するという簡便な操作で再利用可能な形態に復元することができ、更には、特定の薬品洗浄を行うことで、スラリーの粘度調整を容易に行うと共に、ホウ素吸着性能を回復させて再生することができ、劣化吸着剤をホウ素吸着剤として有効に再利用することが可能となる。
本発明によれば、従来、廃棄されていた劣化吸着剤を回収して再利用することができるため、有価物の回収再利用による資源の有効利用、吸着剤コストの低減、廃棄物の減量を図ることができる。
According to the present invention, the boron adsorbent deteriorated by long-term use can be restored to a reusable form by a simple operation of granulating a slurry obtained by dissolving in an organic solvent, By performing specific chemical cleaning, the viscosity of the slurry can be easily adjusted, and the boron adsorption performance can be recovered and regenerated, and the deteriorated adsorbent can be effectively reused as a boron adsorbent. .
According to the present invention, it is possible to recover and reuse a deteriorated adsorbent that has been disposed of in the past. Therefore, it is possible to effectively use resources by collecting and reusing valuable materials, reduce adsorbent costs, and reduce waste. Can be planned.
以下に本発明のホウ素吸着剤のリサイクル方法の実施の形態を詳細に説明する。
以下において、使用することにより劣化したホウ素吸着剤を「劣化吸着剤」と称し、この劣化吸着剤を本発明の方法に従って造粒して得られる造粒体を「再生吸着剤」と称す場合がある。
Embodiments of a method for recycling a boron adsorbent according to the present invention will be described in detail below.
In the following, a boron adsorbent deteriorated by use is referred to as a “deteriorated adsorbent”, and a granulated product obtained by granulating the deteriorated adsorbent according to the method of the present invention may be referred to as a “regenerated adsorbent”. is there.
［ホウ素吸着剤］
まず、本発明で処理対象となるホウ素吸着剤について説明する。
このホウ素吸着剤は、高分子樹脂とホウ素吸着成分である希土類元素水酸化物との混合物よりなる。
[Boron adsorbent]
First, the boron adsorbent to be treated in the present invention will be described.
This boron adsorbent is made of a mixture of a polymer resin and a rare earth element hydroxide which is a boron adsorbing component.
高分子樹脂としては、高耐熱性で水不溶性の高分子樹脂が好ましく、ポリフッ化ビニリデン系樹脂、ポリテトラフルオロエチレン系樹脂等のフッ素系樹脂、ポリビニル系樹脂、アルギン酸塩等の天然高分子及びこれらの誘導体が挙げられる。
これらのなかでも、ポリフッ化ビニリデン樹脂、ポリフッ化ビニリデン６フッ化プロピレン共重合樹脂は、希土類元素水酸化物を高濃度に含有させ易く、水不溶性、耐薬品性にも優れる点において好ましい。
これらの高分子樹脂の数平均分子量は通常５００以上、好ましくは２０００以上である。
ホウ素吸着剤中には、これらの高分子樹脂の１種のみが含まれていてもよく、２種以上が含まれていてもよい。
As the polymer resin, a highly heat-resistant and water-insoluble polymer resin is preferable. Fluorine resins such as polyvinylidene fluoride resin and polytetrafluoroethylene resin, natural polymers such as polyvinyl resin and alginate, and these And derivatives thereof.
Among these, a polyvinylidene fluoride resin and a polyvinylidene fluoride hexafluoride propylene copolymer resin are preferable in that they easily contain a rare earth element hydroxide at a high concentration, and are excellent in water insolubility and chemical resistance.
The number average molecular weight of these polymer resins is usually 500 or more, preferably 2000 or more.
In the boron adsorbent, only one kind of these polymer resins may be contained, or two or more kinds may be contained.
一方、希土類元素水酸化物とは、周期表第３族の希土類元素の水酸化物であって、スカンジウム（Ｓｃ）、イットリウム（Ｙ）、ランタノイド元素である、ランタン（Ｌａ）、セリウム（Ｃｅ）、プラセオジム（Ｐｒ）、ネオジム（Ｎｄ）、プロメチウム（Ｐｍ）、サマリウム（Ｓｍ）、ユウロピウム（Ｅｕ）、カドリニウム（Ｇｄ）、テルビウム（Ｔｂ）、ジスプロシウム（Ｄｙ）、ホルミウム（Ｈｏ）、エルビウム（Ｅｒ）、ツリウム（Ｔｍ）、イッテルビウム（Ｙｂ）、ルテチウム（Ｌｕ）の水酸化物である。
これらのうち、セリウム、特に４価のセリウムの水酸化物を好適に用いることができる。
ホウ素吸着剤中にはこれらの希土類元素水酸化物の１種のみ含まれていてもよく、２種以上が含まれていてもよい。
例えば、水酸化セリウムと水酸化イットリウムの併用も好ましく、その場合、水酸化イットリウムは、水酸化セリウムに対して５重量％以下の量で併用することが好ましい。
On the other hand, the rare earth element hydroxide is a rare earth element hydroxide of Group 3 of the periodic table, which is scandium (Sc), yttrium (Y), lanthanoid element, lanthanum (La), cerium (Ce). , Praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), cadmium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er) , Thulium (Tm), ytterbium (Yb), and lutetium (Lu) hydroxide.
Of these, cerium, particularly tetravalent cerium hydroxide, can be preferably used.
In the boron adsorbent, only one kind of these rare earth element hydroxides may be contained, or two or more kinds may be contained.
For example, the combined use of cerium hydroxide and yttrium hydroxide is also preferable. In that case, it is preferable to use yttrium hydroxide in an amount of 5% by weight or less based on cerium hydroxide.
ホウ素吸着剤は、上記の高分子樹脂１００重量部に対して希土類元素水酸化物を６００重量部以上含むことが好ましい。希土類元素水酸化物の含有量が少ないと十分なホウ素吸着性能を得ることができない。
ホウ素吸着性能の面から希土類元素水酸化物の含有量は多い程有利であるが、希土類元素水酸化物の含有量が多過ぎると、バインダーとしての高分子樹脂量が不足するため、希土類元素水酸化物は高分子樹脂１００重量部に対して５０００重量部以下、特に１０００重量部以下、とりわけ８００重量部以下であることが好ましい。
The boron adsorbent preferably contains 600 parts by weight or more of rare earth element hydroxide with respect to 100 parts by weight of the polymer resin. If the content of rare earth element hydroxide is small, sufficient boron adsorption performance cannot be obtained.
From the standpoint of boron adsorption performance, the higher the content of the rare earth element hydroxide, the more advantageous. However, if the content of the rare earth element hydroxide is too large, the amount of the polymer resin as the binder is insufficient. The oxide is preferably 5000 parts by weight or less, more preferably 1000 parts by weight or less, and particularly preferably 800 parts by weight or less with respect to 100 parts by weight of the polymer resin.
ホウ素吸着剤の形状や大きさには特に制限はなく、例えば、形状については、粒状であってもよく、カラムに充填した際に、ホウ素含有排水が支障なく通過できる形状であれば網状成形体等の成形体であってもよい。
球状ないしは楕円体状の粒状体の場合、その平均粒径は０．２〜５．０ｍｍ程度であることが好ましい。ホウ素吸着剤の平均粒径が０．２ｍｍ未満では、カラム充填密度が高くなって通液抵抗が高くなり、作業性が劣る傾向がある。一方、平均粒径が５．０ｍｍを超えると、ホウ素含有排水とホウ素吸着剤との単位時間当たりの接触面積が少なくなり、結果としてホウ素吸着効率が低下するおそれがある。
There is no particular limitation on the shape and size of the boron adsorbent. For example, the shape may be granular, and if the shape is such that the boron-containing wastewater can pass through without difficulty when packed into the column, a net-like molded product. It may be a molded body such as.
In the case of a spherical or ellipsoidal granular material, the average particle size is preferably about 0.2 to 5.0 mm. When the average particle diameter of the boron adsorbent is less than 0.2 mm, the column packing density increases, the liquid flow resistance increases, and workability tends to be inferior. On the other hand, when the average particle diameter exceeds 5.0 mm, the contact area per unit time between the boron-containing wastewater and the boron adsorbent decreases, and as a result, the boron adsorption efficiency may be reduced.
［溶解工程］
本発明においては、使用により劣化したホウ素吸着剤（劣化吸着剤）を有機溶媒に溶解させて、５０℃換算の粘度（以下、本明細書において、「５０℃換算の粘度」を単に「粘度」と称す。）が２００〜１６００ｃＰのスラリーとし、このスラリーを後述の造粒工程に供する。
[Dissolution process]
In the present invention, a boron adsorbent deteriorated by use (deteriorated adsorbent) is dissolved in an organic solvent, and a viscosity in terms of 50 ° C. (hereinafter referred to as “viscosity in terms of 50 ° C.” is simply “viscosity”). Is made a slurry of 200 to 1600 cP, and this slurry is subjected to a granulation step described later.
造粒工程に供するスラリーの粘度が２００ｃＰより低くても１６００ｃＰを超えても、ホウ素吸着剤として再利用可能な良好な形状に造粒することは困難である。 Even if the viscosity of the slurry used in the granulation step is lower than 200 cP or higher than 1600 cP, it is difficult to granulate into a good shape that can be reused as a boron adsorbent.
劣化吸着剤の溶解に用いる有機溶媒としては、劣化吸着剤に含まれる高分子樹脂の良溶媒であればよく、例えば、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドンなどを用いることができる。これらの有機溶媒は１種を単独で用いてもよく、２種以上を混合して用いてもよい。 The organic solvent used for dissolving the deteriorated adsorbent may be a good solvent for the polymer resin contained in the deteriorated adsorbent. For example, dimethyl sulfoxide, N-methyl-2-pyrrolidone, or the like can be used. These organic solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
劣化吸着剤を有機溶媒に溶解させるには、例えば、劣化吸着剤を有機溶媒に添加して撹拌混合すればよい。その際の有機溶媒の使用量は、予め予備実験を行って、粘度２００〜１６００ｃＰのスラリーが調製できるような量として用いてもよく、この粘度範囲よりも高粘度となる量の有機溶媒を用いて、高粘度のスラリーを調製し、このスラリーに更に有機溶媒を追加添加して粘度２００〜１６００ｃＰのスラリーを調製してもよい。 In order to dissolve the deteriorated adsorbent in the organic solvent, for example, the deteriorated adsorbent may be added to the organic solvent and mixed with stirring. The amount of the organic solvent used in this case may be used as an amount by which a preliminary experiment is performed in advance to prepare a slurry having a viscosity of 200 to 1600 cP, and an organic solvent having an amount higher than this viscosity range is used. A slurry with a high viscosity may be prepared, and an organic solvent may be further added to the slurry to prepare a slurry with a viscosity of 200 to 1600 cP.
劣化吸着剤を有機溶媒に溶解させる際には、有機溶媒を加温してもよく、有機溶媒を加温することにより、有機溶媒への高分子樹脂の溶解を促進することができ、短時間で溶解工程を行うことが可能となる。この場合、有機溶媒の温度は、溶解効率と作業上の安全性等の面から５０〜７０℃程度とすることが好ましい。 When dissolving the deteriorated adsorbent in the organic solvent, the organic solvent may be heated. By heating the organic solvent, the dissolution of the polymer resin in the organic solvent can be promoted for a short time. It becomes possible to perform a dissolution process. In this case, the temperature of the organic solvent is preferably about 50 to 70 ° C. from the viewpoint of dissolution efficiency and work safety.
溶解工程では、劣化吸着剤と有機溶媒とを混合して劣化吸着剤中の高分子樹脂を溶解させ、高分子樹脂の不溶分が確認されず、希土類元素水酸化物紛体が分散した均一なスラリーが得られたら、溶解操作を終了する。 In the dissolution process, the deteriorated adsorbent and the organic solvent are mixed to dissolve the polymer resin in the deteriorated adsorbent, and the insoluble content of the polymer resin is not confirmed, and a uniform slurry in which the rare earth element hydroxide powder is dispersed. Is obtained, the dissolution operation is terminated.
なお、劣化吸着剤中の高分子樹脂が単に物理的に劣化して微細化ないしは収縮しただけではなく、化学的にも劣化して組成変化ないしは分子量低下といった変性を起こしている場合、このような劣化吸着剤を単に有機溶媒に溶解させても、造粒により、ホウ素吸着剤としての使用に耐え得る十分な強度を有する再生吸着剤を得ることができない場合がある。
この場合には、補強のために、劣化していない高分子樹脂の追加添加が必要となり、高分子樹脂の添加で多くの場合、スラリーの粘度が１６００ｃＰを超えてしまう。
そこで、このような場合には、高分子樹脂を添加するのではなく、新品のホウ素吸着剤（劣化していないホウ素吸着剤）或いは、新品の高分子樹脂（劣化していない高分子樹脂）と希土類元素水酸化物を、劣化吸着剤と共に所定の割合で有機溶媒に添加混合することが好ましく、このようにすることにより、得られる再生吸着剤の強度を高めると共に希土類元素水酸化物含有量を確保した上で、スラリー粘度を２００〜１６００ｃＰに調整することが可能となる。
It should be noted that the polymer resin in the deteriorated adsorbent is not only physically deteriorated and refined or shrunk, but also chemically deteriorated to cause modification such as composition change or molecular weight reduction. Even if the deteriorated adsorbent is simply dissolved in an organic solvent, a regenerated adsorbent having sufficient strength to withstand use as a boron adsorbent may not be obtained by granulation.
In this case, it is necessary to add an undegraded polymer resin for reinforcement, and in many cases, the viscosity of the slurry exceeds 1600 cP due to the addition of the polymer resin.
Therefore, in such a case, instead of adding a polymer resin, a new boron adsorbent (undegraded boron adsorbent) or a new polymer resin (undegraded polymer resin) It is preferable to add and mix the rare earth element hydroxide with the deteriorated adsorbent in a predetermined ratio to the organic solvent. By doing so, the strength of the regenerated adsorbent obtained can be increased and the rare earth element hydroxide content can be increased. After securing, the slurry viscosity can be adjusted to 200 to 1600 cP.
また、塩類濃度の高いホウ素含有排水等の処理に使用され、排水由来の塩類等の不純物が吸着ないしは付着している劣化吸着剤を、そのまま有機溶媒に溶解させると、不純物の影響でスラリー粘度が１６００ｃＰを超えてしまう場合がある。有機溶媒の添加量を増やすことで、スラリー粘度を低下させることができるが、有機溶媒量を増加させるとスラリー中の希土類元素水酸化物の含有割合が少なくなり、性能維持の面で好ましくない。
従って、このような場合には、溶解工程に先立ち、以下に記載する薬品による洗浄工程を行って、劣化吸着剤に吸着ないし付着している不純物を予め除去することが好ましく、このような洗浄工程を行うことで、得られる再生吸着剤のホウ素吸着性能も高めることができる。
In addition, when a deteriorated adsorbent, which is used for treatment of boron-containing wastewater with a high salt concentration and is adsorbed or adhering to impurities such as salt derived from wastewater, is dissolved in an organic solvent as it is, the viscosity of the slurry is affected by the impurities. It may exceed 1600 cP. Increasing the amount of the organic solvent can reduce the slurry viscosity, but increasing the amount of the organic solvent decreases the content of rare earth element hydroxide in the slurry, which is not preferable in terms of maintaining performance.
Therefore, in such a case, it is preferable to remove the impurities adsorbed or adhered to the deteriorated adsorbent in advance by performing a cleaning step with chemicals described below prior to the dissolution step. By performing the above, it is possible to improve the boron adsorption performance of the obtained regenerated adsorbent.
このような洗浄を行う場合であっても洗浄を行わない場合であっても、溶解工程に供する劣化吸着剤は水分量が十分に低減されているものであることが好ましい。これは、劣化吸着剤中の水分量が多いと、有機溶媒がこの水分で希釈されて劣化吸着剤中の高分子樹脂が溶解し難くなるためである。従って、溶解工程に供する劣化吸着剤は必要に応じて、後述の乾燥工程で十分に水分量を減少させておくことが好ましい。 Whether the cleaning is performed or not, it is preferable that the deteriorated adsorbent used in the dissolution process has a sufficiently reduced water content. This is because if the amount of water in the deteriorated adsorbent is large, the organic solvent is diluted with this water and the polymer resin in the deteriorated adsorbent becomes difficult to dissolve. Therefore, it is preferable that the amount of water in the deteriorated adsorbent to be used in the dissolution process is sufficiently reduced in the drying process described later as necessary.
［洗浄工程］
溶解工程に先立つ洗浄工程では、酸及び／又はアルカリ、好ましくは酸及びアルカリで劣化吸着剤を洗浄する。酸及びアルカリにより洗浄を行う場合、いずれを先に行ってもよいが、Ｃａ等のスケール成分除去の観点で酸洗浄を先に行い、酸洗浄後にアルカリ洗浄を行うことが好ましい。酸洗浄とアルカリ洗浄は、それぞれ２回以上行うことも可能である。
[Washing process]
In the washing step prior to the dissolution step, the deteriorated adsorbent is washed with acid and / or alkali, preferably acid and alkali. When washing with an acid and an alkali, whichever may be performed first, it is preferable to perform the acid cleaning first from the viewpoint of removing scale components such as Ca, and then perform the alkali cleaning after the acid cleaning. Acid cleaning and alkali cleaning can each be performed twice or more.
酸洗浄に用いる酸としては、塩酸（ＨＣｌ）、硫酸（Ｈ２ＳＯ４）等の無機酸を用いることができ、その濃度としては０．５Ｎ以上、特に２〜５Ｎであることが好ましい。酸濃度が０．５Ｎより低いと、洗浄による十分な不純物除去効果を得ることができず、例えば、以下の通液洗浄の場合、通液量を増やしても洗浄効果が得られない場合がある。酸濃度が５Ｎより高くても、２Ｎの場合と洗浄効果に大差はなく、薬品コストの面で好ましくない。 As the acid used for the acid cleaning, an inorganic acid such as hydrochloric acid (HCl) or sulfuric acid (H 2 SO 4 ) can be used, and its concentration is preferably 0.5 N or more, particularly 2 to 5 N. If the acid concentration is lower than 0.5N, sufficient impurity removal effect by cleaning cannot be obtained. For example, in the case of the following liquid cleaning, the cleaning effect may not be obtained even if the liquid passing amount is increased. . Even if the acid concentration is higher than 5N, the cleaning effect is not significantly different from that of 2N, which is not preferable in terms of chemical cost.
アルカリ洗浄に用いるアルカリとしては、水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）等のアルカリ金属水酸化物を用いることができ、その濃度としては０．５Ｎ以上、特に２〜５Ｎであることが好ましい。アルカリ濃度が０．５Ｎより低いと洗浄による十分な不純物除去効果を得ることができず、例えば、以下の通液洗浄の場合、通液量を増やしても洗浄効果が得られない場合がある。アルカリ濃度が５Ｎより高くても、２Ｎの場合と洗浄効果に大差はなく、薬品コストの面で好ましくない。 As the alkali used for the alkali cleaning, alkali metal hydroxides such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) can be used, and the concentration thereof is 0.5N or more, particularly 2 to 5N. Is preferred. When the alkali concentration is lower than 0.5N, it is not possible to obtain a sufficient impurity removal effect by cleaning. For example, in the case of the following liquid cleaning, the cleaning effect may not be obtained even if the liquid passing amount is increased. Even if the alkali concentration is higher than 5N, the cleaning effect is not significantly different from that of 2N, which is not preferable in terms of chemical cost.
薬品洗浄は、劣化吸着剤を充填したカラムに酸又はアルカリを通液して行うことが好ましく、この場合、十分な洗浄効果を得る上で、酸、アルカリの通液量は、それぞれ２ＢＶ以上であることが好ましい。ただし、酸、アルカリの通液量を過度に多くしても、洗浄効果は頭打ちとなるため、通常その通液量の上限はそれぞれ３ＢＶ以下である。 The chemical cleaning is preferably performed by passing an acid or alkali through a column packed with a deteriorated adsorbent. In this case, in order to obtain a sufficient cleaning effect, the acid and alkali flow rates are 2 BV or more, respectively. Preferably there is. However, even if the acid and alkali flow rates are excessively increased, the cleaning effect reaches its peak, so the upper limit of the flow rate is usually 3 BV or less.
上記の薬品洗浄後に、水洗を行うことが好ましく、例えば、劣化吸着剤を充填したカラムに純水を３〜５ＢＶ程度通水して水洗することが好ましい。 After the above chemical cleaning, it is preferable to perform water cleaning. For example, it is preferable to pass pure water through a column filled with a deteriorated adsorbent for about 3 to 5 BV.
なお、上記の通液洗浄は、上向流で行っても下向流で行ってもよい。 In addition, the above liquid cleaning may be performed in an upward flow or a downward flow.
［乾燥工程］
劣化吸着剤、或いは上記薬品洗浄後の劣化吸着剤を溶解工程に先立ち乾燥する場合、乾燥方法としては、減圧乾燥、加熱乾燥等各種の方法を採用することができるが、簡易な操作で短時間で乾燥することができることから、加熱乾燥が好ましい。加熱により乾燥を行う場合、加熱温度が高い方が乾燥効率の面で好ましいが、乾燥温度が高く６５℃以上となると、高分子樹脂の熱劣化等で有機溶媒への溶解時に粘度が上昇する傾向がある。このため、乾燥温度は６５℃未満、例えば４５〜５５℃とすることが好ましい。
[Drying process]
When drying the deteriorated adsorbent or the deteriorated adsorbent after the chemical washing prior to the dissolving step, various methods such as reduced pressure drying and heat drying can be adopted as drying methods. Heat drying is preferable because it can be dried with When drying by heating, a higher heating temperature is preferable in terms of drying efficiency, but when the drying temperature is higher than 65 ° C., the viscosity tends to increase when dissolved in an organic solvent due to thermal degradation of the polymer resin or the like. There is. For this reason, it is preferable that a drying temperature shall be less than 65 degreeC, for example, 45-55 degreeC.
［造粒工程］
前記の溶解工程で得られた粘度２００〜１６００ｃＰのスラリーを造粒して再生吸着剤を得る。
[Granulation process]
A regenerated adsorbent is obtained by granulating the slurry having a viscosity of 200 to 1600 cP obtained in the dissolving step.
スラリーの造粒方法としては特に制限はないが、水中造粒が望ましい。 Although there is no restriction | limiting in particular as the granulation method of a slurry, Underwater granulation is desirable.
造粒により得られる再生吸着剤の形状としては、ホウ素吸着剤としての使用において、例えばカラムに充填してホウ素含有排水を通液する際に支障なく通液することができるような形状であればよく、特に制限はないが、一般的には、楕円体状ないしは球状のほぼ均一な粒状体であることが好ましく、その平均粒径としては、前述の新品のホウ素吸着剤と同様の理由から０．２〜５．０ｍｍであることが好ましい。 As the shape of the regenerated adsorbent obtained by granulation, in the use as a boron adsorbent, for example, if it is a shape that can be passed without trouble when filling the column and passing the boron-containing wastewater, Although there is no particular limitation, in general, an elliptical or spherical substantially uniform granular material is preferable, and the average particle diameter is 0 for the same reason as the above-mentioned new boron adsorbent. It is preferably 2 to 5.0 mm.
上記の造粒により得られた再生吸着剤は、ホウ素含有排水の処理に有効に再利用することができる。 The regenerated adsorbent obtained by the above granulation can be effectively reused for the treatment of boron-containing waste water.
以下に実施例、比較例及び参考例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, comparative examples, and reference examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
なお、以下の実施例、比較例及び参考例において、再生処理に供した劣化吸着剤は、特開２００４−３３００１２の実施例１に記載の方法で製作した新品のホウ素吸着剤（ポリフッ化ビニリデン−６フッ化プロピレン共重合樹脂（以下「原料ポリマー」と称す。）１００重量部に、水酸化セリウム７００重量部を含む、平均粒径０．７０ｍｍの球状の粒状体）を充填した吸着塔に、石炭焚き脱硫排水を約２年間通液することにより劣化させたものである。
この劣化吸着剤は、原料ポリマーの微細化、収縮により吸着塔において差圧上昇の傾向を示していた。
また、スラリーの造粒は、水中造粒により行い、でき上った造粒体が糸引きがなく、楕円体状ないし球状の粒状造粒体となる場合を、造粒体形状良好（○）と評価した。
In the following Examples, Comparative Examples, and Reference Examples, the deteriorated adsorbent used for the regeneration treatment was a new boron adsorbent (polyvinylidene fluoride-) produced by the method described in Example 1 of JP-A-2004-330012. To an adsorption tower packed with 100 parts by weight of a hexafluoropropylene copolymer resin (hereinafter referred to as “raw polymer”), 700 parts by weight of cerium hydroxide and spherical particles having an average particle size of 0.70 mm, It was deteriorated by passing coal-fired desulfurization effluent for about two years.
This deteriorated adsorbent showed a tendency to increase the differential pressure in the adsorption tower due to the refinement and shrinkage of the raw polymer.
The granulation of the slurry is performed by underwater granulation. When the resulting granule does not have stringing and becomes an ellipsoidal or spherical granular granule, the shape of the granule is good (O). It was evaluated.
また、再生処理により得られた造粒体（再生吸着剤）の吸着性能の評価は以下の方法により行った。
［吸着性能の評価方法］
再生処理により得られた造粒体に対し、アルカリ液による賦活処理を行った後、以下の評価を行った。
純水にＨ３ＢＯ３（試薬１級）を溶解させて初期ホウ素濃度（Ｂ濃度）２００ｍｇ／Ｌにした試験液を調製し、アルカリ（ＮａＯＨ）を添加してｐＨ８．５に調整した。
この試験液１Ｌ中に、賦活させた造粒体２５ｍＬを投入し、ｐＨが８．５±０．１の範囲になるよう酸（ＨＣｌ）又はアルカリ（ＮａＯＨ）で調整しながら９０時間攪拌を行った。その後、上澄液中のホウ素濃度（上澄液Ｂ濃度）を測定し、この測定値から、造粒体（再生吸着剤）単位重量当たりのホウ素吸着量（以下、単に「Ｂ吸着量」と記載する。）を算出した。
Further, the adsorption performance of the granulated material (regenerated adsorbent) obtained by the regeneration treatment was evaluated by the following method.
[Evaluation method of adsorption performance]
The granule obtained by the regeneration treatment was subjected to activation treatment with an alkali solution, and then evaluated as follows.
A test solution was prepared by dissolving H 3 BO 3 (reagent grade 1) in pure water to an initial boron concentration (B concentration) of 200 mg / L, and adjusted to pH 8.5 by adding alkali (NaOH).
In 1 L of this test solution, 25 mL of the activated granule was added, and the mixture was stirred for 90 hours while adjusting with acid (HCl) or alkali (NaOH) so that the pH was in the range of 8.5 ± 0.1. It was. Thereafter, the boron concentration (supernatant B concentration) in the supernatant is measured, and from this measured value, the boron adsorption amount per unit weight of the granulated body (regenerated adsorbent) (hereinafter simply referred to as “B adsorption amount”) To be described).
［実施例１］
直径８０ｍｍのアクリル製カラムに劣化吸着剤５００ｍＬを充填し、２ＮのＨＣｌ水溶液２ＢＶと２ＮのＮａＯＨ水溶液２ＢＶを順次通液して洗浄し、次いで、純水３ＢＶを通水して水洗した後、カラムより抜き出して５０℃に設定した熱風乾燥機中で恒量になるまで乾燥処理を行った。
６５℃に加温したジメチルスルホキシド２４０ｍＬに、上記の乾燥後の吸着剤３００ｇを添加して撹拌混合して溶解させたところ、スラリーの粘度が１３，０５５ｃＰとなった。
そこで、スラリー粘度が１，６００ｃＰ以下になるようにジメチルスルホキシドを６０ｍＬ追加添加し、得られた粘度１，５８１ｃＰのスラリーを平均粒径が０．７ｍｍになるよう造粒したところ、楕円体状ないし球状の粒状造粒体が得られた。
この造粒体の吸着剤としての評価結果を再生処理条件と共に、表１に示した。
[Example 1]
An acrylic column with a diameter of 80 mm is filled with 500 mL of a deteriorated adsorbent, washed with 2N HCl aqueous solution 2BV and 2N NaOH aqueous solution 2BV sequentially, and then washed with pure water 3BV. It was further extracted and dried in a hot air drier set at 50 ° C. until it reached a constant weight.
When 300 g of the above-mentioned adsorbent after drying was added to 240 mL of dimethyl sulfoxide heated to 65 ° C., and stirred and mixed, the viscosity of the slurry was 13,055 cP.
Therefore, 60 mL of dimethyl sulfoxide was added to the slurry so that the slurry viscosity was 1,600 cP or less, and the resulting slurry having a viscosity of 1,581 cP was granulated to have an average particle size of 0.7 mm. A spherical granular granule was obtained.
Table 1 shows the evaluation results of the granules as an adsorbent together with the regeneration treatment conditions.
［実施例２］
直径８０ｍｍのアクリル製カラムに劣化吸着剤５００ｍＬを充填し、０．５ＮのＨＣｌ水溶液２ＢＶと０．５ＮのＮａＯＨ水溶液２ＢＶを順次通液して洗浄し、次いで、純水３ＢＶを通水して水洗した後、カラムより抜き出して５０℃に設定した熱風乾燥機中で恒量になるまで乾燥処理を行った。
６５℃に加温したジメチルスルホキシド２４０ｍＬに、上記の乾燥後の吸着剤３００ｇを添加して撹拌混合して溶解させたところ、スラリーの粘度が１４，０１５ｃＰとなった。
そこで、スラリー粘度が１，６００ｃＰ以下になるようにジメチルスルホキシドを６０ｍＬ追加添加し、得られた粘度１，２２２ｃＰのスラリーを平均粒径が０．７ｍｍになるよう造粒したところ、楕円体状ないし球状の粒状造粒体が得られた。
この造粒体の吸着剤としての評価結果を再生処理条件と共に、表１に示した。
[Example 2]
An acrylic column with a diameter of 80 mm is filled with 500 mL of a deteriorated adsorbent, washed with 0.5N HCl aqueous solution 2BV and 0.5N NaOH aqueous solution 2BV sequentially, and then washed with pure water 3BV. After that, a drying treatment was performed until it became a constant weight in a hot air dryer set at 50 ° C. by extracting from the column.
When 300 g of the above-mentioned adsorbent after drying was added to 240 mL of dimethyl sulfoxide heated to 65 ° C. and stirred and mixed, the viscosity of the slurry was 14,015 cP.
Therefore, 60 mL of dimethyl sulfoxide was added to the slurry so that the slurry viscosity was 1,600 cP or less, and the resulting slurry having a viscosity of 1,222 cP was granulated to have an average particle size of 0.7 mm. A spherical granular granule was obtained.
Table 1 shows the evaluation results of the granules as an adsorbent together with the regeneration treatment conditions.
［実施例３］
実施例１と同様にして劣化吸着剤の酸洗浄、アルカリ洗浄、水洗及び乾燥処理を行った。
得られた乾燥後の吸着剤１５０ｇを、原料ポリマーと水酸化セリウム粉末を新品のホウ素吸着剤と同配合で混合したもの１５０ｇと共に、６５℃に加温したジメチルスルホキシド２４０ｍＬに添加して撹拌混合して溶解させたところ、スラリーの粘度が１，９００ｃＰとなった。
そこで、スラリー粘度が１，６００ｃＰ以下になるようジメチルスルホキシドを１５ｍＬ追加添加し、得られた粘度１，５９７ｃＰのスラリーを平均粒径が０．７ｍｍになるよう造粒したところ、楕円体状ないし球状の粒状造粒体が得られた。
この造粒体の吸着剤としての評価結果を再生処理条件と共に、表１に示した。
[Example 3]
In the same manner as in Example 1, the deteriorated adsorbent was subjected to acid washing, alkali washing, water washing and drying treatment.
150 g of the obtained adsorbent after drying was added to 240 mL of dimethyl sulfoxide heated to 65 ° C. together with 150 g of a raw material polymer and cerium hydroxide powder mixed with a new boron adsorbent in the same composition and mixed with stirring. As a result, the viscosity of the slurry was 1,900 cP.
Accordingly, 15 mL of dimethyl sulfoxide was added to the slurry so that the slurry viscosity was 1,600 cP or less, and the resulting slurry having a viscosity of 1,597 cP was granulated to have an average particle size of 0.7 mm. A granular granule was obtained.
Table 1 shows the evaluation results of the granules as an adsorbent together with the regeneration treatment conditions.
［実施例４］
直径８０ｍｍのアクリル製カラムに劣化吸着剤５００ｍＬを充填し、０．３ＮのＨＣｌ水溶液０．３ＢＶと２ＮのＮａＯＨ水溶液２ＢＶを順次通液して洗浄し、次いで、純水３ＢＶを通水して水洗した後、カラムより抜き出して５０℃に設定した熱風乾燥機中で恒量になるまで乾燥処理を行った。
６５℃に加温したジメチルスルホキシド２４０ｍＬに、上記の乾燥後の吸着剤３００ｇを添加して撹拌混合して溶解させたところ、スラリーの粘度が３２，４４０ｃＰとなった。
そこで、スラリー粘度が１，６００ｃＰ以下になるようにジメチルスルホキシドを１２０ｍＬ追加添加し、得られた粘度１，４１０ｃＰのスラリーを平均粒径が０．７ｍｍになるよう造粒したところ、楕円体状ないし球状の粒状造粒体が得られた。
この造粒体の吸着剤としての評価結果を再生処理条件と共に、表１に示した。
[Example 4]
An acrylic column with a diameter of 80 mm is filled with 500 mL of a deteriorating adsorbent, washed with 0.3N HCl aqueous solution 0.3BV and 2N NaOH aqueous solution 2BV sequentially, and then washed with pure water 3BV. After that, a drying treatment was performed until it became a constant weight in a hot air dryer set at 50 ° C. by extracting from the column.
When 300 g of the above-mentioned adsorbent after drying was added to 240 mL of dimethyl sulfoxide heated to 65 ° C. and dissolved by stirring and mixing, the viscosity of the slurry was 32,440 cP.
Therefore, 120 mL of dimethyl sulfoxide was added to the slurry so that the slurry viscosity was 1,600 cP or less, and the resulting slurry having a viscosity of 1,410 cP was granulated to have an average particle size of 0.7 mm. A spherical granular granule was obtained.
Table 1 shows the evaluation results of the granules as an adsorbent together with the regeneration treatment conditions.
［実施例５］
実施例１と同様にして劣化吸着剤の酸洗浄、アルカリ洗浄及び水洗を行った吸着剤を、６５℃に設定した熱風乾燥機中で恒量になるまで乾燥処理を行った。
６５℃に加温したジメチルスルホキシド２４０ｍＬに、上記の乾燥後の吸着剤３００ｇを添加して撹拌混合して溶解させたところ、スラリーの粘度が４５，３９０ｃＰとなった。
そこで、スラリー粘度が１，６００ｃＰ以下になるようにジメチルスルホキシドを１５０ｍＬ追加添加し、得られた粘度１，５０５ｃＰのスラリーを平均粒径が０．７ｍｍになるよう造粒したところ、楕円体状ないし球状の粒状造粒体が得られた。
この造粒体の吸着剤としての評価結果を再生処理条件と共に、表１に示した。
[Example 5]
The adsorbent that had been subjected to acid washing, alkali washing, and water washing of the deteriorated adsorbent in the same manner as in Example 1 was dried in a hot air drier set at 65 ° C. until it reached a constant weight.
When 300 g of the adsorbent after drying described above was added to 240 mL of dimethyl sulfoxide heated to 65 ° C., and stirred to mix, the viscosity of the slurry was 45,390 cP.
Therefore, 150 mL of dimethyl sulfoxide was added to the slurry so that the slurry viscosity was 1,600 cP or less, and the resulting slurry having a viscosity of 1,505 cP was granulated to have an average particle diameter of 0.7 mm. A spherical granular granule was obtained.
Table 1 shows the evaluation results of the granules as an adsorbent together with the regeneration treatment conditions.
［参考例１］
前記の新品のホウ素吸着剤について、前述の吸着性能の評価を行って結果を表１に示した。
[Reference Example 1]
For the new boron adsorbent, the aforementioned adsorption performance was evaluated and the results are shown in Table 1.
表１より、予め酸洗浄とアルカリ洗浄を行った後乾燥処理した劣化吸着剤を有機溶媒で所定の粘度にスラリー化したものを造粒することにより、劣化吸着剤を再生することができ、特に、０．５Ｎ以上の酸と０．５Ｎ以上のアルカリを用い、また６５℃未満の温度で乾燥することにより劣化吸着剤の吸着性能を十分に回復させることができることが分かる。 From Table 1, it is possible to regenerate the deteriorated adsorbent by granulating a deteriorated adsorbent that has been subjected to acid cleaning and alkali cleaning and then dried and then slurried to a predetermined viscosity with an organic solvent. It can be seen that the adsorption performance of the deteriorated adsorbent can be sufficiently recovered by using an acid of 0.5N or more and an alkali of 0.5N or more and drying at a temperature of less than 65 ° C.
［実施例６、比較例１，２］
実施例１と同様にして劣化吸着剤の酸洗浄、アルカリ洗浄及び水洗を行った吸着剤を、６５℃に設定した熱風乾燥機中で恒量になるまで乾燥処理を行った。
得られた乾燥後の吸着剤を、６５℃に加温したジメチルスルホキシドに所定の割合で添加して撹拌混合することにより、粘度が２，５９０ｃＰ（比較例１）、１，６５０ｃＰ（比較例２）、１，５９７ｃＰ（実施例６）と、粘度の異なる３種類のスラリーを得た。
粘度２，９５０ｃＰの比較例１のスラリーを造粒したところ、造粒体が糸を引いた状態となり長い楕円体形の形状となった。
また、粘度１，６５０ｃＰの比較例２のスラリーの造粒を行ったところ、やはり糸を引いた状態のものが確認された。
これに対して、粘度１，５９７ｃＰの実施例６のスラリーの造粒を行ったところ、糸引きした造粒体は見られず、楕円体状ないし球状の粒状造粒体を得ることができた。
この結果から、スラリーの粘度が１，６００ｃＰ以下であると良好な造粒体が得られることが分かる。
[Example 6, Comparative Examples 1 and 2]
The adsorbent that had been subjected to acid washing, alkali washing, and water washing of the deteriorated adsorbent in the same manner as in Example 1 was dried in a hot air drier set at 65 ° C. until it reached a constant weight.
The obtained adsorbents after drying were added to dimethyl sulfoxide heated to 65 ° C. at a predetermined ratio and mixed by stirring, whereby the viscosities were 2,590 cP (Comparative Example 1) and 1,650 cP (Comparative Example 2). ), 1,597 cP (Example 6), and three types of slurry having different viscosities were obtained.
When the slurry of Comparative Example 1 having a viscosity of 2,950 cP was granulated, the granulated body was in a state where a yarn was pulled, and a long ellipsoidal shape was formed.
Further, when the slurry of Comparative Example 2 having a viscosity of 1,650 cP was granulated, it was confirmed that the yarn was pulled.
On the other hand, when the slurry of Example 6 having a viscosity of 1,597 cP was granulated, no threaded granulation was seen, and an elliptical or spherical granular granule could be obtained. .
From this result, it can be seen that a good granulated product can be obtained when the viscosity of the slurry is 1,600 cP or less.
Claims (6)
該高分子樹脂が劣化したホウ素吸着剤を有機溶媒と混合して該ホウ素吸着剤中の高分子樹脂が溶解したスラリーを得る溶解工程と、
該溶解工程で得られたスラリーを造粒する造粒工程とを有し、
該造粒工程に供するスラリーの５０℃換算の粘度が２００〜１６００ｃＰであることを特徴とするホウ素吸着剤のリサイクル方法。 A polymer resin as a binder, a method for recycling boron adsorbent wherein the polymer resin has degraded contained boron in the adsorbent comprising a mixture of a rare earth element hydroxide is boron adsorbed components,
A melting step of obtaining a slurry polymer resin is dissolved in the boron adsorbent is mixed with an organic solvent a boron adsorbent wherein the polymer resin is deteriorated,
A granulation step of granulating the slurry obtained in the dissolution step,
A method for recycling a boron adsorbent, wherein the slurry subjected to the granulation step has a viscosity in terms of 50 ° C of 200 to 1600 cP.
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