JP3592495B2

JP3592495B2 - Sucrose liquid purifying apparatus and method for regenerating sucrose liquid purifying apparatus

Info

Publication number: JP3592495B2
Application number: JP23225297A
Authority: JP
Inventors: 友二浅川; 伸浅野
Original assignee: Organo Corp
Current assignee: Organo Corp
Priority date: 1997-08-28
Filing date: 1997-08-28
Publication date: 2004-11-24
Anticipated expiration: 2017-08-28
Also published as: JPH1170000A

Description

【０００１】
【発明の属する技術分野】
本発明は、ショ糖液精製装置および同装置の再生方法に関するものである。さらに詳しくは軟化塔とアニオン塔と混床塔を組み合わせたショ糖液精製装置および同装置の再生方法に関するものである。
【０００２】
【従来の技術】
従来から、ショ糖液は、活性炭処理、骨炭処理、イオン交換樹脂処理による脱色処理を行った後、イオン交換樹脂を用いて脱塩処理を行って精製されている。脱塩精製システムとして、ＯＨ形の強塩基性アニオン交換樹脂を用いたアニオン塔と、ＯＨ形の強塩基性アニオン交換樹脂とＨ形の弱酸性カチオン交換樹脂の混床塔を用いる脱塩精製システム（特開平２−２９５４９９号）が提案されている。このシステムは従来の脱塩精製システムであるリバース法や混床法に比べて処理量、脱色率とも優れた脱塩精製システムである。
【０００３】
【発明が解決しようとする課題】
ショ糖液はｐＨが酸性側になるとショ糖が分解するため、ショ糖液の脱塩精製は糖液のｐＨが酸性側にならないように行う必要がある。そのため、ＯＨ形の強塩基性アニオン交換樹脂を用いたアニオン塔とＯＨ形のアニオン交換樹脂とＨ形の弱酸性カチオン交換樹脂の混床塔を組み合わせた上記脱塩システムでは、ショ糖液を始めにＯＨ形のアニオン交換樹脂に接触させてショ糖液のｐＨをアルカリ性とした後、強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂の混床樹脂に接触させて精製を行う。
【０００４】
しかしこの方法ではＯＨ形の強塩基性アニオン交換樹脂との接触において糖液がアルカリ性になるため、カルシウムやマグネシウムなどの硬度成分が比較的多く含まれている糖液を処理する場合には、これらの硬度成分が水酸化物や炭酸化合物として析出して樹脂層内部に沈殿し、イオン交換樹脂の交換基を閉塞して脱塩性能の低下を引き起こしたり、また樹脂層の差圧が上昇する等の問題があった。リバース法でも始めに強塩基性アニオン交換樹脂に接触させて処理を行うため同様の問題が起きる。
【０００５】
その沈積した硬度成分を除去するために、５〜５０サイクルに１回の割合でアニオン交換塔内の強塩基性アニオン交換樹脂を温ＨＣｌ等の酸を用いて回生するのが通常である。しかしながら、通液毎に硬度成分等が樹脂層内部に沈積するため安定した処理にはなりにくい。
【０００６】
本発明が解決しようとする課題は、安定した脱塩精製処理を行うことのできるショ糖液精製装置及び同装置の効率的な再生方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らが、鋭意研究を進めた結果、従来のアニオン塔と混床塔を組み合わせた脱塩精製装置において、前段に軟化塔を設けることにより、上記課題が解決されることを見いだし、本発明を完成するに至った。
【０００８】
すなわち、本発明は、ショ糖液を通液することにより、ショ糖液中のカルシウムイオンやマグネシウムイオン等の硬度成分をナトリウムイオンまたはカリウムイオンに置換するためのナトリウム形またはカリウム形カチオン交換樹脂を充填した軟化塔と、軟化塔を通過した処理液を通液する強塩基性アニオン交換樹脂を充填したアニオン塔と、アニオン塔を通過した処理液を通液する強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂を充填した混床塔とを設けたことを特徴とするショ糖液精製装置、
混床塔の弱酸性カチオン交換樹脂の酸性再生廃液を軟化塔のカチオン交換樹脂に通薬した後、混床塔の強塩基性アニオン交換樹脂のアルカリ性再生廃液および／またはアニオン塔の強塩基性アニオン交換樹脂のアルカリ性再生廃液を軟化塔のカチオン交換樹脂に通薬することを特徴とする請求項１に記載のショ糖液精製装置の再生方法
および混床塔の弱酸性カチオン交換樹脂の酸性再生廃液と、混床塔の強塩基性アニオン交換樹脂のアルカリ性再生廃液および／またはアニオン塔の強塩基性アニオン交換樹脂のアルカリ性再生廃液とを混合して得られる中性再生廃液を軟化塔のカチオン交換樹脂に通薬することを特徴とする請求項１に記載のショ糖液精製装置の再生方法に関するものである。
【０００９】
【発明の実施の形態】
本発明の請求項１に係るショ糖液精製装置は、図１に示すように強塩基性アニオン交換樹脂４を充填したアニオン塔３と強塩基性アニオン交換樹脂および弱酸性カチオン交換樹脂の混合樹脂６を充填した混床塔５からなる装置の前段にカチオン交換樹脂２を充填した軟化塔１を設けたものである。軟化塔に充填するカチオン交換樹脂は、ショ糖液中の硬度成分を吸着できるものであれば特に限定されず、強酸性のものでも弱酸性のものでも使用できるが、強酸性カチオン交換樹脂がカルシウムやマグネシウム等の硬度成分の除去性能に優れている点で好ましい。また、カチオン交換樹脂のイオン形としては、一般的にナトリウム形のものを使用するが、この他にもカリウム形のものを使用することもできる。
【００１０】
本発明のショ糖液精製装置によりショ糖液を精製するには、原料のショ糖液の原液は、軟化塔１の上部から通液され、例えばナトリウム形のカチオン交換樹脂２の層を通り、原液中のカルシウムイオンやマグネシウムイオン等の硬度成分がイオン交換されナトリウムイオンと置換され、その結果、軟化処理後のショ糖液中には、ＮａＣｌ、ＮａＳＯ_４等のナトリウム塩が含まれることになる。軟化塔１の下部から流出した処理液を、アニオン塔３の上部から通液し、ＯＨ形の強塩基性アニオン交換樹脂４層を通り、脱色および脱アニオンされて下部から流出する。原液中のカルシウムイオンやマグネシウムイオン等の硬度成分は前段の軟化塔１のカチオン交換樹脂２に吸着されて除去されているので、アニオン塔３の強塩基性アニオン交換樹脂４に硬度成分が析出して蓄積されることがない。軟化処理後のショ糖液に含まれていたＣｌイオン、ＳＯ_４イオン等の陰イオンは、アニオン塔３のＯＨ形強塩基性アニオン交換樹脂４によってＯＨイオンと置換されるので、アニオン塔処理後のショ糖液中には主としてＮａＯＨが含まれている。アニオン塔３の下部から流出した処理液を、混床塔５の上部から通液し、ＯＨ形の強塩基性アニオン交換樹脂とＨ形の弱酸性カチオン交換樹脂との混合樹脂６層を通り、脱色・脱塩処理されて混床塔５の下部から精製ショ糖液として流出してくる。混床塔５では、アニオン塔３処理後のショ糖液中に含まれているＮａイオンや、該ショ糖液中に微量残留しているカルシウムイオン、マグネシウムイオン等のカチオンは弱酸性カチオン交換樹脂により吸着され、また、該ショ糖液中に微量残留しているＣｌ、ＳＯ_４イオン等のアニオンは強塩基性アニオン交換樹脂によって吸着されて、除去される。
【００１１】
請求項１に記載のショ糖液精製装置は、脱塩処理前に軟化処理を行うことにより、アニオン塔内の強塩基性アニオン交換樹脂へのカルシウムやマグネシウム等の硬度成分の析出、蓄積を防ぐことができ、該強塩基性アニオン交換樹脂の交換基の閉塞による脱塩性能の低下および樹脂塔の差圧上昇を防止することができる。
【００１２】
本発明の請求項１記載のショ糖液精製装置の再生処理は、まず混床塔内の強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂を比重差により分離した後行う。
【００１３】
図２に示すように、分離後の混床塔５にまず塩酸水溶液等の酸再生剤を混床塔５上部から通液し、再生廃液を下部から排出して上層の強塩基性アニオン交換樹脂７と下層の弱酸性カチオン交換樹脂８とに一括して通薬する。酸再生剤の一括通薬により、混床塔５の弱酸性カチオン交換樹脂８が再生（Ｈ形化）され、強塩基性アニオン交換樹脂７が回生処理される。混床塔５から排出された酸性再生廃液を、アニオン塔３の上部から通薬し、アニオン塔３内の強塩基性アニオン交換樹脂４の回生処理を行う。アニオン塔３から排出された酸性再生廃液を、軟化塔１の上部より通薬する。これにより、軟化塔１のカチオン交換樹脂２の一部がＮａ形となり、その他がＨ形となる。すなわち、酸再生剤として例えば塩酸水溶液を使用した場合、酸性再生廃液中には、塩酸によって混床塔の弱酸性カチオン交換樹脂８から脱離したＮａに由来するＮａＣｌと、再生に利用されなかった余剰の塩酸が含まれているのみでその他のＣａ等の不純物イオンは極くわずかしか含まれていないので、これを軟化塔１に通すとカチオン交換樹脂２はその一部がＮａ形、他がＨ形になる。
【００１４】
なお、混床塔５の酸再生剤による一括通薬は、強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂との混合樹脂を分離せずに一括通薬し、その後両イオン交換樹脂を比重分離して、後述の強塩基性アニオン交換樹脂の再生を行うようにしてもよい。
【００１５】
次いで、図３（ａ）に示すように、混床塔５の上部よりＮａＯＨ水溶液等のアルカリ再生剤を通薬し、同時に混床塔５下部より水を導入し、再生廃液を両イオン交換樹脂層のほぼ中間部に設けたコレクター（不図示）から排出させて、混床塔５内の強塩基性アニオン交換樹脂７を再生（ＯＨ形）する。
【００１６】
混床塔５から排出されたアルカリ性再生廃液を軟化塔１の上部から通薬し、カチオン交換樹脂２のうち、Ｈ形になっているカチオン交換樹脂をＮａ形に再生する。
【００１７】
なお、軟化塔１に混床塔５から排出される酸性再生廃液を通薬することなく直接アルカリ性再生廃液を通薬すると、軟化塔１内のカチオン交換樹脂２に吸着されているカルシウムイオンやマグネシウムイオンが水酸化物として析出してしまうので好ましくない。
【００１８】
さらに、図３（ｂ）に示すように、アニオン塔３の上部よりアルカリ再生剤を通薬し、強塩基性アニオン交換樹脂４を再生（ＯＨ形化）する。通常、混床塔５の強塩基性アニオン交換樹脂７の再生時に排出されるアルカリ性再生廃液中には軟化塔１のカチオン交換樹脂２の再生に必要なナトリウム量は充分に含まれているが、もし不足する場合は、アニオン塔３より排出されたアルカリ性再生廃液を軟化塔１上部から通薬してもよい。
【００１９】
再生方法のその他の実施形態として、混床塔５に酸再生剤を通薬する際に、強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂を比重差を利用して分離した後、酸再生剤を混床塔５下部から導入して、下層の弱酸性カチオン交換樹脂８層に酸再生剤を上向流で通薬し、酸性再生廃液をコレクターより排出させてもよい。この場合、同時に混床塔５上部より水を導入し、上層の強塩基性アニオン交換樹脂７層に下降流で水を流してコレクターから排出させる。ただし、強塩基性アニオン交換樹脂を回生処理できる点で、上述の酸再生剤を一括通薬する再生方法が好ましい。
【００２０】
また、混床塔５から排出される酸性再生廃液を、アニオン塔３に導入せず直接軟化塔１に導入してもよい。ただし、アニオン塔３の強塩基性アニオン交換樹脂の回生処理を行える点で、図２に示した方法が好ましい。
【００２１】
図３（ａ）、（ｂ）に示した方法は、軟化塔１のカチオン交換樹脂２をほぼ完全にＮａ形にするために、混床塔５の強塩基性アニオン交換樹脂７のアルカリ性再生廃液と、アニオン塔３の強塩基性アニオン交換樹脂４のアルカリ性再生廃液を用いる例を示したが、いずれか一方のみで軟化塔１のカチオン交換樹脂２を充分Ｎａ形にできる場合は、いずれか一方のアルカリ性再生廃液を使用すればよい。
【００２２】
また、混床塔５から排出される酸性再生廃液、あるいはこの酸性再生廃液をさらにアニオン塔３に通薬して排出される酸性再生廃液と、混床塔５の強塩基性アニオン交換樹脂７のアルカリ性再生廃液およびアニオン塔３のアルカリ性再生廃液の両方あるいはいずれか一方とを混合して中和し、得られた中性廃液を軟化塔１のカチオン交換樹脂２の再生に用いてもよい。
【００２３】
もちろん、軟化塔１のカチオン交換樹脂２を、新品の再生剤（例えば、塩化ナトリウム水溶液等）を用いて再生してもよいが、薬品コストが増大する。
【００２４】
【実施例】
以下、実施例により本発明を詳細に説明するが、実施例により本発明が限定されるものではない。
【００２５】
実施例１
表１に示した原糖液を強酸性カチオン交換樹脂（ロームアンドハース社製、「アンバーライトＩＲ−１２０Ｂ」）２０ｍｌを充填した軟化用カラム（軟化塔）と、強塩基性アニオン交換樹脂（ロームアンドハース社製、「アンバーライトＩＲＡ−４０２ＢＬ」）４０ｍｌを充填したアニオンカラム（アニオン塔）と強塩基性アニオン交換樹脂（ロームアンドハース社製、「アンバーライトＩＲＡ−４０２ＢＬ」）４０ｍｌと弱酸性カチオン交換樹脂（ロームアンドハース社製、「アンバーライトＩＲＣ−７６）２０ｍｌを混合して充填した混床式カラム（混床塔）を用いて、通液温度５０℃、通液流量２００ｍｌ／ｈで２０００ｍｌを処理する操作を１サイクルとして通液を行った。
【００２６】
再生処理としては、はじめに混床式カラム内の強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂を比重差を利用して分離した後、下降流式で１Ｎ−ＨＣｌ（１６０ｍｌ）を混床式カラムに通薬して、強塩基性アニオン交換樹脂の回生と弱酸性カチオン交換樹脂の再生を行った。その酸性再生廃液をアニオンカラムの強塩基性アニオン交換樹脂に通薬して回生した後、軟化用カラムの強酸性カチオン交換樹脂に通薬した。
【００２７】
その後、混床式カラム内の強塩基性アニオン交換樹脂に１Ｎ−ＮａＯＨ（８０ｍｌ）を通薬して強塩基性アニオン交換樹脂を再生し、そのアルカリ性再生廃液を軟化用カラムの強酸性カチオン交換樹脂に通薬した。その後、混床式カラム内の強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂が均等になるように混合した。また、酸性再生廃液通薬後のアニオンカラム内の強塩基性アニオン交換樹脂に１Ｎ−ＮａＯＨ（８０ｍｌ）を通薬して再生し、そのアルカリ性再生廃液を軟化用カラムの強酸性カチオン交換樹脂に通薬した。
【００２８】
上記の方法で、ショ糖液精製処理−再生の操作を繰り返して行った。５サイクル目の軟化処理したショ糖液の性状を表１に示す。
【００２９】
【表１】

【００３０】
表１に示した結果から明かなように、本発明のショ糖液精製装置により処理を行うことにより、前段の軟化塔で硬度成分を予め除去することができ、アニオン塔内の強塩基性アニオン交換樹脂にショ糖液中の硬度成分が析出、蓄積することがないので、アニオン塔内での硬度成分の析出による目詰まりが解消され、色素の脱着、イオン交換処理が容易になり、従来の処理システムより、安定した処理性能が得られる。
【００３１】
また、本発明の再生方法により、軟化塔のカチオン交換樹脂を充分に再生できることが分かる。
【００３２】
比較例１
表１に示した原糖液を強塩基性アニオン交換樹脂（ロームアンドハース社製、「アンバーライトＩＲＡ−４０２ＢＬ」）４０ｍｌを充填したアニオンカラムと、強塩基性アニオン交換樹脂（ロームアンドハース社製、「アンバーライトＩＲＡ−４０２ＢＬ」）４０ｍｌと弱酸性カチオン交換樹脂（ロームアンドハース社製、「アンバーライトＩＲＣ−７６」）２０ｍｌを混合して充填した混床式カラムを用いて、通液温度５０℃、通液流量２００ｍｌ／ｈで２０００ｍｌを処理する操作を１サイクルとして通液を行った。
【００３３】
再生処理としては、はじめに混床式カラム内の強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂を比重差を利用して分離した後、下降流式で１Ｎ−ＨＣｌ（１６０ｍｌ）を混床式カラムに通薬して、塩基性アニオン交換樹脂の回生と弱酸性カチオン交換樹脂の再生を行なった。
【００３４】
その後、混床式カラム内の強塩基性アニオン交換樹脂に１Ｎ−ＮａＯＨ（８０ｍｌ）を通薬して強塩基性アニオン交換樹脂を再生した。その後、混床式カラム内の強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂を均等になるように混合した。同様にアニオンカラムの強塩基性アニオン交換樹脂に１Ｎ−ＮａＯＨ（８０ｍｌ）を通薬して再生した。
【００３５】
上記の方法でショ糖液精製処理−再生処理の操作を繰り返した。３サイクル目にはアニオンカラム内の強塩基性アニオン交換樹脂に肉眼で確認できるほど硬度成分が析出した。
【００３６】
【発明の効果】
本発明のショ糖液精製装置により、アニオン塔の強塩基性アニオン交換樹脂に硬度成分が析出することがなく、ショ糖液の精製を安定して行うことができる。また、本発明の再生方法によれば、混床塔の再生廃液を用いて軟化塔のカチオン交換樹脂を再生することができるので、該カチオン交換樹脂を例えば新品の食塩水溶液を用いて再生する場合に比べて、再生薬品コストを低減することができる。
【図面の簡単な説明】
【図１】本発明のショ糖液精製装置の説明図。
【図２】本発明の再生方法のうち、酸再生剤による再生方法を示すフロー図。
【図３】本発明の再生方法のうち、アルカリ再生剤による再生方法を示すフロー図で、（ａ）は混床塔の強塩基性アニオン交換樹脂の再生と軟化塔のカチオン交換樹脂の再生を示すフロー図で、（ｂ）はアニオン塔の強塩基性アニオン交換樹脂の再生と軟化塔のカチオン交換樹脂の再生を示すフロー図。
【符号の説明】
１軟化塔
２カチオン交換樹脂
３アニオン塔
４強塩基性アニオン交換樹脂
５混床塔
６強塩基性アニオン交換樹脂と弱酸性カチオン交換樹脂との混合樹脂
７強塩基性アニオン交換樹脂
８弱酸性カチオン交換樹脂[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a sucrose liquid refining apparatus and a method for regenerating the same. More particularly, the present invention relates to a sucrose liquid refining apparatus in which a softening tower, an anion tower, and a mixed bed tower are combined, and a method for regenerating the same.
[0002]
[Prior art]
BACKGROUND ART Conventionally, a sucrose solution has been purified by performing a decolorizing treatment by an activated carbon treatment, a bone char treatment, and an ion exchange resin treatment, and then performing a desalting treatment by using an ion exchange resin. As a desalination purification system, a desalination purification system using an anion column using a strong basic anion exchange resin in the OH form and a mixed bed tower of a strong basic anion exchange resin in the OH form and a weakly acidic cation exchange resin in the H form (JP-A-2-295499) has been proposed. This system is a desalination and purification system that is superior in both throughput and decolorization rate as compared with the conventional desalination and purification systems such as the reverse method and the mixed bed method.
[0003]
[Problems to be solved by the invention]
Since sucrose decomposes when the pH of the sucrose solution becomes acidic, desalting and purification of the sucrose solution must be performed so that the pH of the sucrose solution does not become acidic. Therefore, in the above desalination system combining an anion column using an OH type strongly basic anion exchange resin and a mixed bed column of an OH type anion exchange resin and an H type weakly acidic cation exchange resin, a sucrose solution is used. After making the pH of the sucrose solution alkaline by contacting it with an anion exchange resin in the form of OH, the mixture is contacted with a mixed bed resin of a strongly basic anion exchange resin and a weakly acidic cation exchange resin for purification.
[0004]
However, in this method, the sugar solution becomes alkaline upon contact with a strong basic anion exchange resin in the OH form, and therefore, when a sugar solution containing a relatively large amount of a hardness component such as calcium or magnesium is treated, these sugar solutions are used. Hardness component precipitates as a hydroxide or carbonate compound and precipitates inside the resin layer, blocking the exchange groups of the ion exchange resin, causing a decrease in desalination performance, and an increase in the differential pressure of the resin layer, etc. There was a problem. Even in the reverse method, a similar problem occurs because the treatment is performed by first contacting with a strong basic anion exchange resin.
[0005]
In order to remove the deposited hardness component, the strong basic anion exchange resin in the anion exchange tower is usually regenerated using an acid such as hot HCl at a rate of once every 5 to 50 cycles. However, a stable treatment is unlikely to be performed because a hardness component or the like is deposited inside the resin layer for each liquid passage.
[0006]
The problem to be solved by the present invention is to provide a sucrose liquid purifying apparatus capable of performing a stable desalination purification treatment and an efficient regeneration method of the apparatus.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive research and found that the above-mentioned problem can be solved by providing a softening tower in the former stage in a conventional desalination and purification apparatus combining an anion tower and a mixed bed tower. The invention has been completed.
[0008]
That is, the present invention provides a sodium- or potassium-type cation exchange resin for replacing hardness components such as calcium ions and magnesium ions in a sucrose solution with sodium ions or potassium ions by passing a sucrose solution. A packed softening tower, an anion tower filled with a strong basic anion exchange resin that allows the processing liquid to pass through the softening tower, and a strong basic anion exchange resin that allows the processing liquid to pass through the anion tower and weak acidity A sucrose liquid purification apparatus, which is provided with a mixed bed tower filled with a cation exchange resin,
After the acidic regeneration waste liquid of the weakly acidic cation exchange resin in the mixed bed tower is passed through the cation exchange resin of the softening tower, the alkaline regeneration waste liquid of the strongly basic anion exchange resin in the mixed bed tower and / or the strong basic anion of the anion tower 2. The method for regenerating a sucrose solution purifying apparatus according to claim 1, wherein the alkaline regeneration waste liquid of the exchange resin is passed through the cation exchange resin of the softening tower, and the acidic regeneration waste liquid of the weakly acidic cation exchange resin in the mixed bed tower. And a neutral regeneration waste liquid obtained by mixing an alkaline regeneration waste liquid of the strongly basic anion exchange resin of the mixed bed tower and / or an alkaline regeneration waste liquid of the strongly basic anion exchange resin of the anion tower with the cation exchange resin of the softening tower. 2. A method for regenerating a sucrose solution refining apparatus according to claim 1, wherein
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The sucrose liquid purifying apparatus according to claim 1 of the present invention comprises an anion tower 3 filled with a strongly basic anion exchange resin 4, a mixed resin of a strongly basic anion exchange resin and a weakly acidic cation exchange resin as shown in FIG. A softening tower 1 filled with a cation exchange resin 2 is provided at the front stage of an apparatus composed of a mixed bed tower 5 filled with 6. The cation exchange resin to be filled in the softening tower is not particularly limited as long as it can adsorb the hardness component in the sucrose solution, and a strongly acidic or weakly acidic cation exchange resin can be used. It is preferable because it has excellent performance in removing hardness components such as magnesium and magnesium. As the ionic form of the cation exchange resin, a sodium form is generally used, but a potassium form can also be used.
[0010]
In order to purify the sucrose solution with the sucrose solution purifying apparatus of the present invention, the stock solution of the raw material sucrose solution is passed through the upper part of the softening tower 1 and, for example, passes through a layer of the cation exchange resin 2 in the form of sodium. Hardness components such as calcium ions and magnesium ions in the stock solution are ion-exchanged and replaced with sodium ions. As a result, the sucrose solution after the softening treatment contains sodium salts such as NaCl and NaSO _4. . The treatment liquid flowing out from the lower part of the softening tower 1 is passed through the upper part of the anion tower 3, passes through four layers of the strongly basic anion exchange resin in the OH form, is decolorized and deanionized, and flows out from the lower part. Since the hardness components such as calcium ions and magnesium ions in the stock solution are adsorbed and removed by the cation exchange resin 2 of the softening tower 1 in the former stage, the hardness components precipitate on the strongly basic anion exchange resin 4 of the anion tower 3. No accumulation. Anions such as Cl ions and SO ₄ ions contained in the sucrose solution after the softening treatment are replaced with OH ions by the OH type strong basic anion exchange resin 4 of the anion tower 3. The sucrose solution contains mainly NaOH. The treatment liquid flowing out from the lower part of the anion tower 3 flows through the upper part of the mixed bed tower 5 and passes through a mixed resin 6 layer of an OH type strongly basic anion exchange resin and an H type weakly acidic cation exchange resin, It is decolorized and desalted and flows out from the lower part of the mixed bed tower 5 as a purified sucrose solution. In the mixed bed tower 5, Na ions contained in the sucrose solution after the treatment with the anion tower 3 and cations such as calcium ions and magnesium ions tracely remaining in the sucrose solution are weakly acidic cation exchange resins. And anions such as Cl and SO ₄ ions, which are trace amounts remaining in the sucrose solution, are adsorbed and removed by the strong basic anion exchange resin.
[0011]
The sucrose liquid refining apparatus according to claim 1 performs softening treatment before desalting treatment, thereby preventing precipitation and accumulation of hardness components such as calcium and magnesium on the strongly basic anion exchange resin in the anion tower. Thus, it is possible to prevent a decrease in desalination performance and an increase in pressure difference in the resin tower due to blocking of the exchange group of the strong basic anion exchange resin.
[0012]
The regeneration treatment of the sucrose liquid purifying apparatus according to the first aspect of the present invention is performed after first separating the strongly basic anion exchange resin and the weakly acidic cation exchange resin in the mixed bed tower by a specific gravity difference.
[0013]
As shown in FIG. 2, an acid regenerant such as an aqueous hydrochloric acid solution is first passed through the mixed bed tower 5 from the upper part of the mixed bed tower 5 after separation, and the regenerated waste liquid is discharged from the lower part. 7 and the lower layer weakly acidic cation exchange resin 8 are passed through at once. Due to the simultaneous passage of the acid regenerant, the weakly acidic cation exchange resin 8 in the mixed bed tower 5 is regenerated (formed into an H form), and the strongly basic anion exchange resin 7 is regenerated. The acidic regeneration waste liquid discharged from the mixed bed tower 5 is passed through the upper part of the anion tower 3 to carry out regenerative treatment of the strongly basic anion exchange resin 4 in the anion tower 3. The acidic regeneration waste liquid discharged from the anion tower 3 is passed through the upper part of the softening tower 1. Thereby, a part of the cation exchange resin 2 of the softening tower 1 becomes the Na type, and the others become the H type. That is, when, for example, an aqueous hydrochloric acid solution was used as the acid regenerating agent, NaCl derived from Na desorbed from the weakly acidic cation exchange resin 8 of the mixed-bed tower by hydrochloric acid in the acidic regeneration waste liquid was not used for the regeneration. Since only excess hydrochloric acid is contained and only a small amount of other impurity ions such as Ca is contained, when this is passed through the softening tower 1, the cation exchange resin 2 is partially Na-type, and other H-shaped.
[0014]
In addition, in the batch flow of the mixed bed tower 5 with the acid regenerant, the batch flow is carried out without separating the mixed resin of the strongly basic anion exchange resin and the weakly acidic cation exchange resin, and then both ion exchange resins are separated by specific gravity. Then, regeneration of a strongly basic anion exchange resin described later may be performed.
[0015]
Next, as shown in FIG. 3 (a), an alkaline regenerant such as an aqueous solution of NaOH is passed through the upper portion of the mixed bed tower 5, and water is introduced from the lower portion of the mixed bed tower 5 at the same time. The strongly basic anion exchange resin 7 in the mixed bed tower 5 is regenerated (OH form) by discharging from a collector (not shown) provided substantially in the middle of the bed.
[0016]
The alkaline regeneration waste liquid discharged from the mixed bed tower 5 is passed through the upper part of the softening tower 1 to regenerate the H-type cation exchange resin among the cation exchange resins 2 into the Na form.
[0017]
When the alkaline regenerated waste liquid is directly passed through the softening tower 1 without passing the acidic regenerated waste liquid discharged from the mixed bed tower 5, calcium ions and magnesium adsorbed on the cation exchange resin 2 in the softening tower 1 are discharged. It is not preferable because ions are precipitated as hydroxide.
[0018]
Further, as shown in FIG. 3B, an alkali regenerant is passed through the upper part of the anion tower 3 to regenerate (OH form) the strongly basic anion exchange resin 4. Usually, the amount of sodium necessary for the regeneration of the cation exchange resin 2 of the softening tower 1 is sufficiently contained in the alkaline regeneration waste liquid discharged at the time of regeneration of the strongly basic anion exchange resin 7 of the mixed bed tower 5, If it is insufficient, the alkaline regeneration waste liquid discharged from the anion tower 3 may be passed through the upper part of the softening tower 1 as a chemical.
[0019]
As another embodiment of the regeneration method, when the acid regenerant is passed through the mixed-bed tower 5, the strongly basic anion exchange resin and the weakly acidic cation exchange resin are separated using a specific gravity difference, and then the acid regenerant is separated. May be introduced from the lower part of the mixed bed tower 5, and the acid regenerating agent may be passed through the lower layer of the weakly acidic cation exchange resin 8 in an upward flow, and the acidic regenerated waste liquid may be discharged from the collector. In this case, water is simultaneously introduced from the upper part of the mixed bed tower 5, and water is caused to flow downward through the upper layer of the strongly basic anion exchange resin 7 and discharged from the collector. However, the regeneration method in which the above-mentioned acid regenerant is passed through at once is preferable in that the strongly basic anion exchange resin can be regenerated.
[0020]
Further, the acidic regeneration waste liquid discharged from the mixed bed tower 5 may be directly introduced into the softening tower 1 without being introduced into the anion tower 3. However, the method shown in FIG. 2 is preferable in that the regeneration treatment of the strongly basic anion exchange resin in the anion tower 3 can be performed.
[0021]
In the method shown in FIGS. 3A and 3B, in order to almost completely convert the cation exchange resin 2 of the softening tower 1 into the Na form, the alkaline regeneration waste liquid of the strongly basic anion exchange resin 7 of the mixed bed tower 5 is used. And an example in which an alkaline regenerating waste liquid of the strongly basic anion exchange resin 4 of the anion tower 3 is used. In the case where the cation exchange resin 2 of the softening tower 1 can be sufficiently made into the Na form by only one of them, one of them is used. May be used.
[0022]
Further, the acidic regeneration waste liquid discharged from the mixed bed tower 5, or the acidic regeneration waste liquid discharged by further passing this acidic regeneration waste liquid through the anion tower 3, and the strong basic anion exchange resin 7 of the mixed bed tower 5 The alkaline regeneration waste liquid and / or the alkaline regeneration waste liquid of the anion tower 3 may be mixed and neutralized by mixing, and the resulting neutral waste liquid may be used for the regeneration of the cation exchange resin 2 of the softening tower 1.
[0023]
Of course, the cation exchange resin 2 of the softening tower 1 may be regenerated using a new regenerant (for example, an aqueous solution of sodium chloride), but the chemical cost increases.
[0024]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
[0025]
Example 1
A softening column (softening tower) in which the raw sugar solution shown in Table 1 was filled with 20 ml of a strongly acidic cation exchange resin (“Amberlite IR-120B” manufactured by Rohm and Haas Co.), and a strongly basic anion exchange resin (Rohm Anion column (anion tower) packed with 40 ml of “Amberlite IRA-402BL” manufactured by Andhase Company, 40 ml of strong basic anion exchange resin (“Amberlite IRA-402BL” manufactured by Rohm and Haas Company) and weakly acidic cation Using a mixed bed column (mixed bed tower) filled with 20 ml of an exchange resin (manufactured by Rohm and Haas Co., Ltd., “Amberlite IRC-76”), 2000 ml at a flowing temperature of 50 ° C. and a flowing flow rate of 200 ml / h were used. The liquid was passed through the operation of treating as one cycle.
[0026]
In the regeneration treatment, first, a strong basic anion exchange resin and a weakly acidic cation exchange resin in a mixed bed column are separated by using a specific gravity difference, and then 1N-HCl (160 ml) is mixed with a down flow type column in a mixed bed column. To regenerate the strongly basic anion exchange resin and regenerate the weakly acidic cation exchange resin. The acidic regeneration waste liquid was passed through a strongly basic anion exchange resin of an anion column to regenerate, and then passed through a strongly acidic cation exchange resin of a softening column.
[0027]
Thereafter, 1N-NaOH (80 ml) is passed through the strongly basic anion exchange resin in the mixed bed type column to regenerate the strongly basic anion exchange resin, and the alkaline regenerated waste liquid is used as the strongly acidic cation exchange resin in the softening column. I passed the medicine. Thereafter, the strongly basic anion exchange resin and the weakly acidic cation exchange resin in the mixed bed column were mixed so as to be uniform. Also, 1N-NaOH (80 ml) is passed through the strongly basic anion exchange resin in the anion column after passing the acidic regeneration waste liquid, and the alkaline regeneration waste liquid is passed through the strongly acidic cation exchange resin of the softening column. I took the medicine.
[0028]
By the above method, the operation of sucrose solution purification treatment-regeneration was repeated. Table 1 shows the properties of the softened sucrose solution at the fifth cycle.
[0029]
[Table 1]

[0030]
As is clear from the results shown in Table 1, by performing the treatment with the sucrose liquid purifying apparatus of the present invention, the hardness component can be removed in advance in the softening tower in the former stage, and the strong basic anion in the anion tower is obtained. Since the hardness component in the sucrose solution does not precipitate and accumulate on the exchange resin, clogging due to the precipitation of the hardness component in the anion tower is eliminated, the desorption of the dye, the ion exchange treatment becomes easy, Stable processing performance can be obtained from the processing system.
[0031]
Further, it can be seen that the cation exchange resin of the softening tower can be sufficiently regenerated by the regenerating method of the present invention.
[0032]
Comparative Example 1
An anion column in which the raw sugar solution shown in Table 1 was filled with 40 ml of a strongly basic anion exchange resin (“Amberlite IRA-402BL” manufactured by Rohm and Haas), and a strongly basic anion exchange resin (manufactured by Rohm and Haas) , "Amberlite IRA-402BL") and 20 ml of a weakly acidic cation exchange resin ("Amberlite IRC-76" manufactured by Rohm and Haas Co.) were mixed and packed using a mixed-bed column, and the liquid passing temperature was 50%. The operation was performed at 2000 ° C. with a flow rate of 200 ml / h at 2000 ° C. as one cycle, and the flow was performed.
[0033]
In the regeneration treatment, first, a strong basic anion exchange resin and a weakly acidic cation exchange resin in a mixed bed column are separated by using a specific gravity difference, and then 1N-HCl (160 ml) is mixed with a down flow type column in a mixed bed column. To recover the basic anion exchange resin and regenerate the weakly acidic cation exchange resin.
[0034]
Thereafter, 1N-NaOH (80 ml) was passed through the strongly basic anion exchange resin in the mixed bed type column to regenerate the strongly basic anion exchange resin. Thereafter, the strongly basic anion exchange resin and the weakly acidic cation exchange resin in the mixed bed column were mixed so as to be uniform. Similarly, 1N-NaOH (80 ml) was passed through the strongly basic anion exchange resin of the anion column to regenerate.
[0035]
The operation of sucrose solution purification treatment-regeneration treatment was repeated by the above method. In the third cycle, a hard component was deposited on the strongly basic anion exchange resin in the anion column so as to be visually confirmed.
[0036]
【The invention's effect】
The sucrose liquid purifying apparatus of the present invention can stably purify a sucrose liquid without depositing a hard component on the strongly basic anion exchange resin of the anion tower. Further, according to the regeneration method of the present invention, the cation exchange resin of the softening tower can be regenerated by using the regeneration waste liquid of the mixed bed tower, so that the cation exchange resin is regenerated using, for example, a new salt solution. As compared with the above, the cost of the regenerated chemical can be reduced.
[Brief description of the drawings]
FIG. 1 is an explanatory view of a sucrose solution purifying apparatus of the present invention.
FIG. 2 is a flowchart showing a regeneration method using an acid regenerant in the regeneration method of the present invention.
FIG. 3 is a flowchart showing a regeneration method using an alkali regenerant among the regeneration methods of the present invention. FIG. 3 (a) shows regeneration of a strongly basic anion exchange resin in a mixed-bed column and regeneration of a cation exchange resin in a softening column. (B) is a flow chart showing regeneration of a strongly basic anion exchange resin in an anion tower and regeneration of a cation exchange resin in a softening tower.
[Explanation of symbols]
Reference Signs List 1 Softening tower 2 Cation exchange resin 3 Anion tower 4 Strongly basic anion exchange resin 5 Mixed bed tower 6 Mixed resin of strongly basic anion exchange resin and weakly acidic cation exchange resin 7 Strongly basic anion exchange resin 8 Weakly acidic cation exchange resin

Claims

By passing a sucrose solution, a softening tower filled with a sodium or potassium cation exchange resin for replacing hardness components such as calcium ions and magnesium ions in the sucrose solution with sodium ions or potassium ions , An anion tower filled with a strong basic anion exchange resin that allows the processing solution to pass through the softening tower, and a strong basic anion exchange resin and a weakly acidic cation exchange resin that allows the processing solution to pass through the anion tower were filled. A sucrose liquid refining device comprising a mixed bed tower.

After the acidic regeneration waste liquid of the weakly acidic cation exchange resin in the mixed bed tower is passed through the cation exchange resin in the softening tower, the alkaline regeneration waste liquid of the strongly basic anion exchange resin in the mixed bed tower and / or the strong basic anion in the anion tower The method for regenerating a sucrose solution purifying apparatus according to claim 1, wherein the alkaline regenerated waste liquid of the exchange resin is passed through the cation exchange resin of the softening tower.

Mixing the acidic regeneration waste liquid of the weakly acidic cation exchange resin in the mixed bed tower, the alkaline regeneration waste liquid of the strongly basic anion exchange resin in the mixed bed tower and / or the alkaline regeneration waste liquid of the strongly basic anion exchange resin in the anion tower The method for regenerating a sucrose liquid purifying apparatus according to claim 1, wherein the obtained neutral regeneration waste liquid is passed through a cation exchange resin in a softening tower.