JP4096891B2 - Regeneration method of anion exchange resin adsorbed thiocyanate ion - Google Patents
Regeneration method of anion exchange resin adsorbed thiocyanate ion Download PDFInfo
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- JP4096891B2 JP4096891B2 JP2004038359A JP2004038359A JP4096891B2 JP 4096891 B2 JP4096891 B2 JP 4096891B2 JP 2004038359 A JP2004038359 A JP 2004038359A JP 2004038359 A JP2004038359 A JP 2004038359A JP 4096891 B2 JP4096891 B2 JP 4096891B2
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- 239000003957 anion exchange resin Substances 0.000 title claims description 47
- 238000011069 regeneration method Methods 0.000 title claims description 38
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 title claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 41
- -1 thiocyanate ions Chemical class 0.000 claims description 37
- 230000008929 regeneration Effects 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012492 regenerant Substances 0.000 claims description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 7
- 230000001172 regenerating effect Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 108010057081 Merozoite Surface Protein 1 Proteins 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Description
本発明は、チオシアン酸イオンを吸着したアニオン交換樹脂の再生方法、特に他のアニオンとともにチオシアン酸イオンを吸着したアニオン交換樹脂を安全かつ効率的に再生する方法に関するものである。 The present invention relates to a method for regenerating an anion exchange resin having adsorbed thiocyanate ions, and more particularly to a method for safely and efficiently regenerating an anion exchange resin having adsorbed thiocyanate ions together with other anions.
石油精製その他のプロセスでは、硫化水素その他の酸成分を含む酸性ガスが発生する。このような酸性ガスは、アルカノールアミン等のアミン液と接触させることにより、酸成分を吸収させて除去する処理方法で処理され、再使用されている。ここで使用するアミン液は酸成分の吸収が進むと吸収能力が低下するので、アニオン交換樹脂と接触させて吸収能力を回復している。吸収能力の回復に使用したアニオン交換樹脂は、通常水酸化ナトリウム水溶液のようなアルカリにより再生して再使用している。ところがアニオン交換樹脂の再生において、アニオン交換樹脂がチオシアン酸イオンを吸着せず、他のアニオンのみを吸着している場合は、水酸化ナトリウム水溶液のような水酸化アルカリにより容易に再生されるが、アニオン交換樹脂がチオシアン酸イオンを吸着している場合は、アルカリ性ではチオシアン酸イオンの吸着力が強いためと推測されるが、水酸化アルカリにより再生することは容易ではなく、チオシアン酸イオンの脱着は不完全になる。 In oil refining and other processes, acid gases containing hydrogen sulfide and other acid components are generated. Such acidic gas is treated and reused by a treatment method that absorbs and removes the acid component by contacting with an amine solution such as alkanolamine. Since the amine solution used here has a reduced absorption capacity as the acid component is absorbed, it is brought into contact with an anion exchange resin to recover the absorption capacity. The anion exchange resin used to recover the absorption capacity is usually regenerated and reused with an alkali such as an aqueous sodium hydroxide solution. However, in the regeneration of anion exchange resin, when the anion exchange resin does not adsorb thiocyanate ions and adsorbs only other anions, it is easily regenerated with an alkali hydroxide such as an aqueous sodium hydroxide solution. If the anion exchange resin adsorbs thiocyanate ions, it is presumed that the alkalinity has a strong adsorptivity of thiocyanate ions, but it is not easy to regenerate with alkali hydroxide, and desorption of thiocyanate ions is not possible. Become imperfect.
特許文献１には、チオシアン酸イオンを吸着したアニオン交換樹脂を、食塩水溶液と接触させた後、水酸化ナトリウム水溶液と接触させて再生する方法が示されており、これによりチオシアン酸イオンの脱着が進み、これによりチオシアン酸イオンを吸着したアニオン交換樹脂を容易に再生できるとされている。しかしながらアニオン交換樹脂を食塩水溶液と接触させると、アニオン交換樹脂はＣｌ形になる。Ｃｌ形の交換基で使用すると、チオシアン酸イオンその他のアニオンが吸着除去される代わりに、塩化物イオンがアミン液中に脱離して腐食の原因となる。このためＣｌ形の交換基をＯＨ形にする必要があるが、アニオン交換樹脂に対するＣｌイオンの結合力が大きいので、Ｃｌ形の交換基をＯＨ形に変換するためには多量の水酸化ナトリウムが必要となる。またチオシアン酸イオンを吸着したアニオン交換樹脂を、食塩水溶液と接触させると、脱着したチオシアン酸イオンはチオシアン酸ナトリウム等の塩となって溶出するが、チオシアン酸塩は酸性または酸性に近い中性では分解してシアンを発生するおそれがあり、安全性に問題がある。
本発明の課題は、チオシアン酸イオンを吸着したアニオン交換樹脂を安全かつ効率的に再生することができるアニオン交換樹脂の再生方法を提案することである。 An object of the present invention is to propose a method for regenerating an anion exchange resin capable of safely and efficiently regenerating an anion exchange resin having adsorbed thiocyanate ions.
本発明は、次のチオシアン酸イオンを吸着したアニオン交換樹脂の再生方法である。
（１）チオシアン酸イオンを吸着したアニオン交換樹脂を、炭酸水素ナトリウム水溶液と接触させて１次再生した後、水酸化ナトリウム水溶液と接触させて２次再生することを特徴とするチオシアン酸イオンを吸着したアニオン交換樹脂の再生方法。
（２）アニオン交換樹脂が、酸性ガス処理用のアミン液の吸収能力回復に用いられてチオシアン酸イオンを吸着した樹脂である上記（１）記載の方法。
（３）３〜１０重量％炭酸水素ナトリウム水溶液を、再生剤量３〜８０ｅｑ／Ｌ−樹脂、通水速度ＳＶ＝５〜４０／ｈｒで樹脂層に通液して１次再生する上記（１）または（２）記載の方法。
（４）３〜１０重量％水酸化ナトリウム水溶液を、再生剤量５〜２０ｅｑ／Ｌ−樹脂、通水速度ＳＶ＝５〜４０／ｈｒで樹脂層に通液して２次再生する上記（１）ないし（３）のいずれかに記載の方法。
The present invention is a method for regenerating an anion exchange resin adsorbing the following thiocyanate ions.
(1) Adsorption of thiocyanate ions, characterized in that the anion exchange resin adsorbed with thiocyanate ions is first regenerated by bringing it into contact with an aqueous sodium hydrogen carbonate solution and then secondarily regenerating by bringing it into contact with an aqueous sodium hydroxide solution. Of regenerating anion exchange resin.
(2) The method according to (1) above, wherein the anion exchange resin is a resin that has been used to recover the absorption capacity of an amine liquid for acid gas treatment and has adsorbed thiocyanate ions.
(3) The above-mentioned (1) primary regeneration by passing a 3 to 10% by weight aqueous sodium hydrogen carbonate solution through the resin layer at a regenerant amount of 3 to 80 eq / L-resin and a water flow rate SV = 5 to 40 / hr. ) Or (2).
(4) A 3 to 10 wt% aqueous sodium hydroxide solution is passed through the resin layer at a regenerant amount of 5 to 20 eq / L-resin and a water flow rate SV of 5 to 40 / hr to perform secondary regeneration (1 ) To (3).
本発明において、再生の対象となるチオシアン酸イオンを吸着したアニオン交換樹脂は、酸性ガス処理に用いられたアミン液の吸収能力回復のためなどに用いられて、チオシアン酸イオンを吸着したアニオン交換樹脂であり、特に他のアニオンとともにチオシアン酸イオンを吸着したアニオン交換樹脂が再生の対象として好ましい。アニオン交換樹脂としては、チオシアン酸イオンおよび他のアニオンを交換吸着できるものであればよく、弱塩基性アニオン交換樹脂でもよいが、中性塩分解能を有する強塩基性アニオン交換樹脂、例えば第四アンモニウム基を有する強塩基性アニオン交換樹脂が好ましい。 In the present invention, the anion exchange resin that adsorbs thiocyanate ions to be regenerated is used to recover the absorption capacity of the amine liquid used in the acid gas treatment, and the anion exchange resin that adsorbs thiocyanate ions. In particular, an anion exchange resin that adsorbs thiocyanate ions together with other anions is preferable as a regeneration target. The anion exchange resin is not particularly limited as long as it can exchange and adsorb thiocyanate ions and other anions, and may be a weakly basic anion exchange resin, but a strong basic anion exchange resin having a neutral salt resolution, such as quaternary ammonium. Strongly basic anion exchange resins having groups are preferred.
チオシアン酸イオンを吸着したアニオン交換樹脂としては、特に限定されないが、石油精製その他のプロセスにおいて酸性ガス処理に用いられたアルカノールアミン等のアミン液の吸収能力回復に用いられることによってチオシアン酸イオンを吸着したものが再生の対象として好ましい。酸性ガス処理が行われるプロセスとしては、石油精製の他に、木材のパルプ化、天然ガスや原油の生産および種々の化学工程や工業プロセスなどが挙げられる。アミン液としては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジグリコールアミン、メチルジエタノールアミンなどのアルカノールアミンが挙げられるが、他のアミンでもよい。またアミンでなく、廃水その他の水溶液からチオシアン酸イオンその他のイオンを吸着したものでもよい。 The anion exchange resin that adsorbs thiocyanate ion is not particularly limited, but adsorbs thiocyanate ion by recovering the absorption capacity of amine liquid such as alkanolamine used for acid gas treatment in petroleum refining and other processes. What was done is preferable as a subject of reproduction. Processes in which acid gas treatment is performed include, in addition to petroleum refining, wood pulping, production of natural gas and crude oil, various chemical processes and industrial processes. Examples of the amine liquid include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, diglycolamine, and methyldiethanolamine, but other amines may be used. Further, thiocyanate ions or other ions may be adsorbed from waste water or other aqueous solutions instead of amines.
本発明において、チオシアン酸イオンを吸着したアニオン交換樹脂の再生は、アニオン交換樹脂からチオシアン酸イオンその他のイオンを脱着して、アニオン交換樹脂のアニオン交換能を回復するために行われる。アニオン交換能の回復により、アニオン交換樹脂はアミンその他の液からチオシアン酸イオンその他のイオンを除去するために使用される。この場合、アニオン交換樹脂はＯＨ形に再生されることにより、チオシアン酸イオンその他のイオンに対するアニオン交換能が回復する。 In the present invention, the regeneration of the anion exchange resin having adsorbed thiocyanate ions is performed in order to desorb thiocyanate ions and other ions from the anion exchange resin to restore the anion exchange ability of the anion exchange resin. By recovering the anion exchange capacity, the anion exchange resin is used to remove thiocyanate ions and other ions from amine and other liquids. In this case, the anion exchange resin is regenerated to the OH form, so that the anion exchange ability for thiocyanate ions and other ions is restored.
本発明の再生方法では、チオシアン酸イオンを吸着したアニオン交換樹脂を、炭酸水素ナトリウム水溶液と接触させて１次再生した後、水酸化ナトリウム水溶液と接触させて２次再生し、アニオン交換樹脂を再生する。１次再生液としての炭酸水素ナトリウム水溶液は、３〜１０重量％、好ましくは５〜７重量％の濃度の水溶液を用いるのが好ましい。接触方法は、浸漬法、流動接触法などでもよいが、カラム通水式の接触方法が好ましく、チオシアン酸イオンを吸着したアニオン交換樹脂層に、再生剤量３〜８０ｅｑ／Ｌ−樹脂、通水速度ＳＶ＝５〜４０／ｈｒで通液して１次再生することができる。 In the regeneration method of the present invention, the anion exchange resin having adsorbed thiocyanate ions is brought into primary regeneration by bringing it into contact with an aqueous sodium hydrogen carbonate solution, and then secondary regeneration is brought into contact with an aqueous sodium hydroxide solution to regenerate the anion exchange resin. To do. The aqueous sodium hydrogen carbonate solution as the primary regeneration solution is preferably an aqueous solution having a concentration of 3 to 10% by weight, preferably 5 to 7% by weight. The contact method may be a dipping method, a fluid contact method, or the like, but a column-water contact method is preferable, and an anion exchange resin layer that has adsorbed thiocyanate ions has a regenerant amount of 3 to 80 eq / L-resin, water flow. Primary regeneration can be performed by passing the liquid at a speed SV = 5 to 40 / hr.
２次再生液としての水酸化ナトリウム水溶液は、３〜１０重量％、好ましくは４〜８重量％の濃度の水溶液を用いるのが好ましい。接触方法は、浸漬法、流動接触法などでもよいが、カラム通水式の接触方法が好ましく、チオシアン酸イオンを吸着したアニオン交換樹脂層に、再生剤量５〜２０ｅｑ／Ｌ−樹脂、通水速度ＳＶ＝５〜４０／ｈｒで通液して２次再生することができる。これにより１次再生でＨＣＯ3形になったアニオン交換樹脂は、２次再生によりＯＨ形に再生される。再生剤量を増やせば、樹脂の初期交換容量まで再生することが可能となる。 The aqueous sodium hydroxide solution as the secondary regeneration solution is preferably an aqueous solution having a concentration of 3 to 10% by weight, preferably 4 to 8% by weight. The contact method may be a dipping method, a fluid contact method, or the like, but a column-water contact method is preferable. Secondary regeneration can be performed by passing liquid at a speed SV = 5 to 40 / hr. As a result, the anion exchange resin that has become HCO 3 form by primary regeneration is regenerated to OH form by secondary regeneration. If the amount of the regenerant is increased, it is possible to regenerate up to the initial exchange capacity of the resin.
強アルカリ性ではチオシアン酸イオンの吸着力が強いため、水酸化アルカリにより再生するとチオシアン酸イオンの脱着は不完全になるが、炭酸水素ナトリウム水溶液で１次再生すると、弱アルカリ性のためチオシアン酸イオンの吸着力が弱くなり、大部分のチオシアン酸イオンは脱着してＨＣＯ3形になる。特許文献１のように食塩で１次再生するとチオシアン酸イオンの脱着性はよいが、Ｃｌ形は樹脂に対する結合力が強いため２次再生でＯＨ形に再生するのは困難であるのに対し、ＨＣＯ3形は結合力が弱いので、水酸化ナトリウム水溶液による２次再生で容易にＯＨ形に変換することができ、交換基をＯＨ形に変換するための水酸化ナトリウム量は少なくなる。食塩で１次再生する場合は、再生剤量を増やしても樹脂の初期交換容量までの再生は難しい。 In strong alkalinity, the thiocyanate ion adsorbing power is strong, so desorption of thiocyanate ion is incomplete when it is regenerated with alkali hydroxide, but when it is first regenerated with aqueous sodium hydrogen carbonate solution, the thiocyanate ion adsorbs due to weak alkalinity The force is weakened and most of the thiocyanate ions are desorbed to form HCO 3 . When the primary regeneration is performed with sodium chloride as in Patent Document 1, the desorbability of thiocyanate ions is good, but the Cl form has a strong binding force to the resin, so it is difficult to regenerate to the OH form by secondary regeneration. Since the HCO 3 form has a weak binding force, it can be easily converted to the OH form by secondary regeneration with an aqueous sodium hydroxide solution, and the amount of sodium hydroxide for converting the exchange group to the OH form is reduced. In the case of primary regeneration with salt, regeneration to the initial exchange capacity of the resin is difficult even if the amount of the regenerant is increased.
チオシアン酸イオンを吸着したアニオン交換樹脂を、炭酸水素ナトリウム水溶液と接触させると、脱着したチオシアン酸イオンはチオシアン酸ナトリウムとなって溶出するが、炭酸水素ナトリウムも流出するため弱アルカリ性であり、チオシアン酸塩の分解によるシアン発生の危険性はない。このため食塩で１次再生する場合に、チオシアン酸塩が分解してシアンを発生するおそれがあるのに比べ、安全性は高い。 When an anion exchange resin that adsorbs thiocyanate ions is brought into contact with an aqueous sodium hydrogen carbonate solution, the desorbed thiocyanate ions are eluted as sodium thiocyanate, but sodium hydrogen carbonate also flows out and is weakly alkaline. There is no danger of cyanide generation due to salt decomposition. For this reason, in the case of primary regeneration with sodium chloride, the safety is high as compared to the possibility that thiocyanate decomposes to generate cyanide.
こうして１次再生および２次再生した後、水（純水）による押出、水洗工程を行って残留する再生液や溶離物を排出し、再生を終了する。再生を終ったアニオン交換樹脂は再び吸着工程に移行し、アミン液等と接触させてチオシアン酸イオンを他のアニオンとともに吸着させる。この場合、アニオン交換樹脂は１次再生により結合したＨＣＯ3は２次再生により脱離してＯＨ形に変換しているため、アニオン交換樹脂からアミン液等に不純物が溶離することはなく、吸着処理によりアミン液等を汚染することなく、アミン液等から不純物アニオンを吸着除去することができる。 After primary regeneration and secondary regeneration in this way, extrusion with water (pure water) and water washing steps are performed to discharge the remaining regeneration solution and eluate, and the regeneration ends. The anion exchange resin that has been regenerated moves to the adsorption process again and is brought into contact with an amine solution or the like to adsorb thiocyanate ions together with other anions. In this case, since the HCO 3 bound by the primary regeneration is desorbed and converted to the OH form by the secondary regeneration, impurities are not eluted from the anion exchange resin into the amine liquid, etc. Thus, the impurity anions can be adsorbed and removed from the amine liquid or the like without contaminating the amine liquid or the like.
なお、上記の１次再生および２次再生の前または後に、他の処理を行い、再生をさらに効率よくすることは可能である。 It should be noted that other processing can be performed before or after the primary reproduction and secondary reproduction described above to further improve the reproduction.
本発明によれば、チオシアン酸イオンを吸着したアニオン交換樹脂を、炭酸水素ナトリウム水溶液と接触させて１次再生した後、水酸化ナトリウム水溶液と接触させて２次再生することにより、チオシアン酸イオンを吸着したアニオン交換樹脂を安全かつ効率的に再生することができる。 According to the present invention, an anion exchange resin having adsorbed thiocyanate ions is brought into primary regeneration by bringing it into contact with an aqueous sodium hydrogen carbonate solution, and then brought into contact with an aqueous sodium hydroxide solution to carry out secondary regeneration. The adsorbed anion exchange resin can be regenerated safely and efficiently.
以下、本発明の実施例について説明する。実施例はアニオン交換樹脂をカラムに充填して、吸着および再生を行った例である。実施例中、％は重量％である。 Examples of the present invention will be described below. In this example, an anion exchange resin is packed in a column and adsorption and regeneration are performed. In the examples,% is% by weight.
実施例１〜３：
内径15mm、高さ200mmのカラムを使用し、ダウケミカル日本株式会社製の強塩基性アニオン交換樹脂DOWEX MSA-1を5mＬ充填した。模擬試料液として、ジイソプロパノールアミン(DIPA)27%にチオシアン酸を6000mg/Ｌ相当添加したものを、通液量100mＬ、通水速度SV=5/hrで通液し、チオシアン酸イオンを吸着させた。再生方法は１次再生液として6％の炭酸水素ナトリウム水溶液を7〜72eq/L-樹脂、通水速度SV=40/hrで通液後、２次再生液として4％の水酸化ナトリウム水溶液を10eq/L−樹脂、通水速度SV=40/hrで通液した。その後、純水を樹脂の80容量分通液して洗浄した。再生剤量とチオシアン酸の脱着量の関係を表１に示す。
Examples 1-3:
Using a column having an inner diameter of 15 mm and a height of 200 mm, 5 mL of strongly basic anion exchange resin DOWEX MSA-1 manufactured by Dow Chemical Japan Co., Ltd. was packed. As a simulated sample solution, thiocyanic acid equivalent to 6000 mg / L added to diisopropanolamine (DIPA) 27% was passed at a flow rate of 100 mL and a water flow rate of SV = 5 / hr to adsorb thiocyanate ions. It was. The regeneration method is as follows: 6% sodium bicarbonate aqueous solution as the primary regeneration solution is 7 to 72 eq / L-resin at a water flow rate of SV = 40 / hr, then 4% sodium hydroxide aqueous solution is used as the secondary regeneration solution. The solution was passed through 10 eq / L-resin at a water flow rate of SV = 40 / hr. Thereafter, 80 volumes of pure water was passed through and washed. Table 1 shows the relationship between the amount of the regenerant and the amount of thiocyanate desorbed.
比較例１：
比較例１として4％の水酸化ナトリウム水溶液を80eq/L―樹脂、通水速度SV=40/hrで通液し、その後、純水を樹脂の80容量分通液して洗浄した場合の結果を表１に示す。
Comparative Example 1:
As a comparative example 1, a 4% sodium hydroxide aqueous solution was passed through 80 eq / L-resin at a water flow rate of SV = 40 / hr, and then purified water was passed through 80 volumes of the resin and washed. Is shown in Table 1.
比較例２：
実施例１〜３において、１次再生液として２０％の塩化ナトリウム水溶液を
６８eq/L-樹脂、通水速度SV=40/hrで通液後、２次再生液として4％の水酸化ナトリウム水溶液を10eq/L−樹脂、通水速度SV=40/hrで通液した。その後、純水を樹脂の80容量分通液して洗浄した。再生剤量とチオシアン酸の脱着量の関係を表２に示す。
Comparative Example 2:
In Examples 1 to 3, after passing a 20% aqueous sodium chloride solution as a primary regeneration solution at 68 eq / L-resin at a water flow rate of SV = 40 / hr, a 4% aqueous sodium hydroxide solution as a secondary regeneration solution. Was passed through at 10 eq / L-resin at a water flow rate of SV = 40 / hr. Thereafter, 80 volumes of pure water was passed through and washed. Table 2 shows the relationship between the amount of the regenerant and the amount of thiocyanate desorbed.
表１より、再生剤量を水酸化ナトリウムと同程度使用すれば、樹脂の初期交換容量程度まで性能が回復することが解る。この場合、水酸化ナトリウムを単独で使用する場合（比較例１）と比較して、少ない再生剤量で同程度まで性能が回復することが解る。また表２より、表１において樹脂の初期交換容量まで性能が１００％回復する実施例３とほぼ同程度の塩化ナトリウム水溶液を用いても、交換容量は２／３程度しか回復できないことがわかる。 From Table 1, it can be seen that if the amount of the regenerant is used as much as sodium hydroxide, the performance is recovered to the initial exchange capacity of the resin. In this case, it can be seen that the performance is restored to the same extent with a small amount of the regenerant compared with the case where sodium hydroxide is used alone (Comparative Example 1). Also, from Table 2, it can be seen that the exchange capacity can be recovered only about 2/3 even when using a sodium chloride aqueous solution of about the same level as in Example 3 whose performance is 100% recovered to the initial exchange capacity of the resin in Table 1.
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