JPS6260943B2 - - Google Patents
Info
- Publication number
- JPS6260943B2 JPS6260943B2 JP55077176A JP7717680A JPS6260943B2 JP S6260943 B2 JPS6260943 B2 JP S6260943B2 JP 55077176 A JP55077176 A JP 55077176A JP 7717680 A JP7717680 A JP 7717680A JP S6260943 B2 JPS6260943 B2 JP S6260943B2
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- ion exchange
- resin layer
- cleaning
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 68
- 239000003456 ion exchange resin Substances 0.000 claims description 61
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 61
- 238000004140 cleaning Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 33
- 239000012670 alkaline solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000003957 anion exchange resin Substances 0.000 description 15
- 230000002378 acidificating effect Effects 0.000 description 13
- 239000003729 cation exchange resin Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- -1 sodium carboxylate Chemical class 0.000 description 5
- 239000008234 soft water Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 229940023913 cation exchange resins Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Description
【発明の詳細な説明】
本発明はアルカリ性溶液で処理したイオン交換
樹脂の洗浄方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for cleaning ion exchange resins treated with an alkaline solution.
従来、イオン交換樹脂をアルカリ性溶液で処理
した後、そのイオン交換樹脂を洗浄するに際して
は、イオン交換樹脂層の残留アルカリ溶液を押出
水で比較的低流速下で置換する操作を行なつた
後、洗浄水で比較的高流速下で洗浄する操作を実
施するが、この洗浄に長時間を要することが多
い。たとえばイオン交換樹脂としてアニオン交換
樹脂を用いる場合は、長期間の使用によりアニオ
ン交換樹脂がカルボン酸基（−COOH）を有す
る有機物で汚染されたり、また用いるアニオン交
換樹脂が特にアクリル系の弱塩基性アニオン交換
樹脂においては、長期間の使用により交換基の一
部が分解されてカルボン酸基が生成されるが、こ
のようなカルボン酸基を有するアニオン交換樹脂
にアルカリ性溶液、たとえばか性ソーダ溶液を通
薬すると交換基はOH形に再生されるが、前述の
カルボン酸基はNaOHと(1)式のように反応してナ
トリウム塩（−COONa）になる。ところがこの
カルボン酸ナトリウムは洗浄工程において(2)式の
ように加水分解して、いつまでもか性ソーダが系
外に出るために、長時間の洗浄が必要になる。 Conventionally, after treating an ion exchange resin with an alkaline solution, when cleaning the ion exchange resin, the residual alkaline solution in the ion exchange resin layer is replaced with extrusion water at a relatively low flow rate. Although washing with washing water is performed at a relatively high flow rate, this washing often takes a long time. For example, when using an anion exchange resin as an ion exchange resin, the anion exchange resin may become contaminated with organic substances having carboxylic acid groups (-COOH) due to long-term use, or the anion exchange resin used may be particularly weakly basic, such as acrylic. In anion exchange resins, when used for a long period of time, some of the exchange groups decompose and carboxylic acid groups are generated. However, if an anion exchange resin containing such carboxylic acid groups is treated with an alkaline solution, such as a caustic soda solution, When passed through the drug, the exchange group is regenerated into the OH form, but the aforementioned carboxylic acid group reacts with NaOH as shown in formula (1) to form a sodium salt (-COONa). However, this sodium carboxylate is hydrolyzed as shown in equation (2) during the washing process, and caustic soda is left out of the system indefinitely, necessitating a long period of washing.
Ｒ−COOH＋NaOH→Ｒ−COONa＋H2O …(1)
Ｒ−COONa＋H2O→Ｒ−COOH＋NaOH …(2)
従来この洗浄を短縮するために、原水をＨ形の
強酸性カチオン交換樹脂で処理することにより得
られる酸性軟水で洗浄しているが、洗浄水にたと
え酸性軟水を用いてもアニオン交換樹脂がアルカ
リ性溶液の通薬によりOH形となつているので、
アニオン交換樹脂層の上部でこの酸性軟水中の
酸、たとえば塩酸が(3)式のように吸着されて純水
となるため、中層部あるいは下層部のアニオン交
換樹脂からは相変わらず前記した(2)式の反応によ
りか性ソーダが溶出するので洗浄時間を短縮する
効果がほとんどない。 R-COOH+NaOH→R-COONa+H 2 O...(1) R-COONa+H 2 O→R-COOH+NaOH...(2) Conventionally, in order to shorten this cleaning process, raw water was treated with H-type strongly acidic cation exchange resin. The resulting acidic soft water is used for cleaning, but even if acidic soft water is used as the cleaning water, the anion exchange resin remains in the OH form due to the passage of the alkaline solution.
The acid in this acidic soft water, such as hydrochloric acid, is adsorbed in the upper part of the anion exchange resin layer as shown in equation (3) and becomes pure water, so the above-mentioned (2) Since caustic soda is eluted by the reaction of the formula, there is almost no effect in shortening the cleaning time.
Ｒ≡NHOH＋HCl→Ｒ≡NHHCl＋H2O …(3)
またイオン交換樹脂として強酸性カチオン交換
樹脂を用い、当該カチオン交換樹脂をアルカリ性
溶液で処理した後の洗浄も長時間を要することも
判明した。 R≡NHOH+HCl→R≡NHHCl+H 2 O (3) It has also been found that when a strongly acidic cation exchange resin is used as the ion exchange resin, it takes a long time to wash the cation exchange resin after treating it with an alkaline solution.
強酸性カチオン交換樹脂をアルカリ性溶液で処
理することはまれではあるが、たとえばNa形、
NH4形などの塩形の強酸性カチオン交換樹脂を用
いる復水処理装置においては、交換基を塩形とす
る際に、法律により固体のみしか入手できない食
塩を用いるよりは単に希釈するのみで使用が可能
なか性ソーダ溶液あるいは炭酸ナトリウム溶液あ
るいはアンモニア水などを用いることがある。 Although it is rare to treat strongly acidic cation exchange resins with alkaline solutions, for example, Na-type,
In condensate treatment equipment that uses a strongly acidic cation exchange resin in the form of a salt such as NH 4 , when the exchange group is in the salt form, it is better to simply dilute it than to use common salt, which by law can only be obtained in solid form. Caustic soda solution, sodium carbonate solution, ammonia water, etc. that can be used may be used.
また復水処理装置で用いた強酸性カチオン交換
樹脂が鉄汚染を受けた際に、亜硫酸塩溶液で処理
し、鉄を還元作用で除去することもあるが、亜硫
酸塩溶液はアルカリ性を示す。 Furthermore, when the strongly acidic cation exchange resin used in the condensate treatment equipment is contaminated with iron, it is sometimes treated with a sulfite solution to remove the iron through its reducing action, but the sulfite solution exhibits alkalinity.
このように強酸性カチオン交換樹脂をアルカリ
性溶液で処理した場合も、前述のアニオン交換樹
脂の場合と同じように洗浄効果が悪く、洗浄に長
時間を要することが判明した。 It has been found that even when a strongly acidic cation exchange resin is treated with an alkaline solution, the cleaning effect is poor and cleaning takes a long time, as in the case of the anion exchange resin described above.
本発明は以上に述べたようなアルカリ性溶液で
処理したイオン交換樹脂を効果的に洗浄し、洗浄
時間を大幅に短縮することを目的とするもので、
イオン交換樹脂をアルカリ性溶液で処理した後に
洗浄するにあたり、イオン交換樹脂層のアルカリ
性溶液を押出水で置換した後、当該イオン交換樹
脂層に小量の酸を添加した直後にイオン交換樹脂
層を混合するか、あるいは当該イオン交換樹脂層
に小量の酸を添加しながらイオン交換樹脂層を混
合し、その後に洗浄水でイオン交換樹脂層を洗浄
することを特徴とするイオン交換樹脂の洗浄方法
に関するものである。 The purpose of the present invention is to effectively clean ion exchange resins treated with an alkaline solution as described above, and to significantly shorten the cleaning time.
When cleaning the ion exchange resin after treating it with an alkaline solution, replace the alkaline solution in the ion exchange resin layer with extrusion water, and then mix the ion exchange resin layer immediately after adding a small amount of acid to the ion exchange resin layer. Or, it relates to a method for cleaning an ion exchange resin, characterized in that the ion exchange resin layer is mixed while adding a small amount of acid to the ion exchange resin layer, and then the ion exchange resin layer is washed with cleaning water. It is something.
以下に本発明を詳細に説明する。 The present invention will be explained in detail below.
純水製造装置、脱塩水製造装置、ホルマリン精
製装置、糖液の脱塩装置などに使用されているア
ニオン交換樹脂、あるいは前述のようなアルカリ
性溶液で塩形にして用いる復水処理装置のカチオ
ン交換樹脂などは所定の通水あるいは通液が終了
した後、アニオン交換樹脂あるいはカチオン交換
樹脂をか性ソーダ溶液あるいはアルカリ性溶液で
処理する、いわゆる再生操作を行なう。この再生
はアニオン交換樹脂の場合は通水あるいは通液工
程で塩形となつた交換基をOH形とする操作であ
り、また復水処理装置のカチオン交換樹脂の場合
は通水においてイオン交換樹脂粒子に沈着した酸
化鉄を塩酸などに浸漬して溶解した後、Ｈ形とな
つた交換基をアルカリ性溶液で塩形とする操作、
あるいは亜硫酸塩溶液で処理してイオン交換樹脂
粒子に沈着した酸化鉄を還元除去する操作であ
る。これらの再生操作は常法によりイオン交換樹
脂層を逆洗、沈整し、次いで1N前後の濃度のか
性ソーダ溶液あるいはアルカリ性溶液を通薬す
る。その後通薬の流速とほぼ同じ流速で充填イオ
ン交換樹脂量とほぼ同量の押出水をイオン交換樹
脂層に流し、イオン交換樹脂層に残留しているか
性ソーダ溶液あるいはアルカリ性溶液を置換す
る。従来の再生操作においては次いで酸性軟水あ
るいは純水を洗浄水とし、当該洗浄水をSV10〜
20の比較的高流速でイオン交換樹脂層に流す洗浄
工程を行なつていたが、前述のように本洗浄に長
時間を要する。 Anion exchange resin used in pure water production equipment, desalinated water production equipment, formalin purification equipment, sugar solution desalination equipment, etc., or cation exchange in condensate treatment equipment used in salt form with an alkaline solution as mentioned above. After a predetermined amount of water or liquid has passed through the resin, the anion exchange resin or cation exchange resin is treated with a caustic soda solution or an alkaline solution, a so-called regeneration operation. In the case of anion exchange resins, this regeneration is an operation in which the exchange group that has become a salt form during the water flow or liquid flow process is converted into the OH form, and in the case of cation exchange resins in condensate treatment equipment, the ion exchange resin is After immersing the iron oxide deposited on the particles in hydrochloric acid or the like to dissolve it, the H-form exchange group is converted into a salt form with an alkaline solution;
Alternatively, the iron oxide deposited on the ion exchange resin particles is reduced and removed by treatment with a sulfite solution. In these regeneration operations, the ion exchange resin layer is backwashed and settled by a conventional method, and then a caustic soda solution or an alkaline solution with a concentration of about 1N is passed through it. Thereafter, an amount of extruded water approximately equal to the amount of the filled ion exchange resin is flowed through the ion exchange resin layer at approximately the same flow rate as the flow rate of the drug, to replace the caustic soda solution or alkaline solution remaining in the ion exchange resin layer. In conventional regeneration operations, acidic soft water or pure water is then used as the wash water, and the wash water is rated at SV10~
The cleaning process was performed by flowing the ion exchange resin layer at a relatively high flow rate of 20°C, but as mentioned above, the main cleaning takes a long time.
本発明においてはイオン交換樹脂層に残留して
いるか性ソーダ溶液あるいはアルカリ性溶液を押
出水で置換した後、以下のような操作を行なう。
すなわち当該イオン交換樹脂層に小量の酸を添加
し、その直後にイオン交換樹脂層を混合するか、
あるいは小量の酸を添加しながらイオン交換樹脂
層を混合するのである。なお添加する酸としては
1N〜2Nの比較的濃度の濃い塩酸、硫酸などの鉱
酸を用いることが好ましいが、場合によつては酢
酸などの比較的分子量の小さい有機酸を用いても
さしつかえない。また酸の使用量は一般にイオン
交換容量の1/10〜1/100の量を用いる。すなわち
イオン交換容量が1.6eq／lRであれば、0.16〜
0.016eq／lRの酸を用いるとよい。なお洗浄性の
善しあしの程度により当該範囲内で適当な量の酸
を使用するが、あまり多量の酸を用いると、アニ
オン交換樹脂の場合は通薬工程において生成させ
たOH形の交換基を塩形としてしまい、またカチ
オン交換樹脂の場合は通薬工程において生成させ
た塩形の交換基をＨ形としてしまうので好ましく
なく、したがつてイオン交換容量の1/10以上の酸
は使用しないことが望ましい。 In the present invention, after replacing the caustic soda solution or alkaline solution remaining in the ion exchange resin layer with extrusion water, the following operations are performed.
That is, adding a small amount of acid to the ion exchange resin layer and mixing the ion exchange resin layer immediately after that, or
Alternatively, the ion exchange resin layer is mixed while adding a small amount of acid. The acid to be added is
It is preferable to use a mineral acid such as hydrochloric acid or sulfuric acid with a relatively high concentration of 1N to 2N, but in some cases, an organic acid with a relatively small molecular weight such as acetic acid may also be used. The amount of acid used is generally 1/10 to 1/100 of the ion exchange capacity. In other words, if the ion exchange capacity is 1.6eq/lR, 0.16~
It is recommended to use 0.016eq/lR acid. An appropriate amount of acid is used within the range depending on the degree of cleaning properties, but if too much acid is used, the OH type exchange group generated during the drug passing process may occur in the case of anion exchange resin. In the case of cation-exchange resins, the salt-form exchange group generated in the drug passing process becomes H-form, which is undesirable. Therefore, do not use acids with a capacity of 1/10 or more of the ion-exchange capacity. This is desirable.
次に当該酸をイオン交換樹脂層に添加するにあ
たつては、添加した酸をイオン交換樹脂層全体に
分散させることが必要である。そのためには酸を
添加した直後にイオン交換樹脂層を混合するか、
あるいはイオン交換樹脂層に酸を添加しながらイ
オン交換樹脂層を混合する。たとえば充填イオン
交換樹脂層に酸を通過させたり、または充填イオ
ン交換樹脂層の一部分のみに酸を接触させたりす
ると、イオン交換樹脂層の一部分のみで酸が吸着
されてしまい所期の目的を達することができな
い。したがつて本発明では酸を添加した直後にイ
オン交換樹脂層を混合するか、あるいはイオン交
換樹脂層に酸を添加しながら混合するが、本発明
においては後者の方がより効果的である。なおイ
オン交換樹脂層を混合する場合、水による逆洗、
機械的撹拌による混合、空気混合などを行なう
が、混合効率のよい空気混合が最も好ましい。こ
のようにしてイオン交換樹脂層を混合し、添加し
た酸をイオン交換樹脂層全体に分散させた後、イ
オン交換樹脂層を沈整し、その後に常法により洗
浄水でイオン交換樹脂層を洗浄すると、洗浄廃水
のアルカリのリーク量を著しく低下させることが
でき、洗浄時間を大幅に短縮することができる。
本発明の作用はイオン交換樹脂層全体に酸を分散
させることにより、カチオン交換樹脂およびアニ
オン交換樹脂共にイオン交換樹脂粒子内あるいは
粒子間の空隙に残留しているアルカリが添加した
酸と瞬時に中和反応を起こすためと考えられ、さ
らにイオン交換樹脂がアニオン交換樹脂の場合
は、前述した(1)式の反応によつて生成したカルボ
ン酸ナトリウムと、添加した酸（たとえば塩酸）
とが(4)式のように反応してカルボン酸となるた
め、あるいはOH形の交換基と添加した酸とが反
応して生成した塩形の交換基と、カルボン酸ナト
リウムとが(5)式のようにイオン交換粒子内の拡散
反応によりカルボン酸となるためと考えられる。 Next, when adding the acid to the ion exchange resin layer, it is necessary to disperse the added acid throughout the ion exchange resin layer. To do this, either mix the ion exchange resin layer immediately after adding the acid, or
Alternatively, the ion exchange resin layer is mixed while adding an acid to the ion exchange resin layer. For example, if an acid is passed through a filled ion exchange resin layer, or if the acid is brought into contact with only a portion of the filled ion exchange resin layer, the acid will be adsorbed by only a portion of the ion exchange resin layer, and the desired purpose will not be achieved. I can't. Therefore, in the present invention, the ion exchange resin layer is mixed immediately after adding the acid, or the ion exchange resin layer is mixed while adding the acid, but the latter is more effective in the present invention. When mixing the ion exchange resin layer, backwashing with water,
Mixing by mechanical stirring, air mixing, etc. may be performed, but air mixing is most preferred as it provides good mixing efficiency. After mixing the ion exchange resin layer in this way and dispersing the added acid throughout the ion exchange resin layer, the ion exchange resin layer is settled, and then the ion exchange resin layer is washed with washing water using a conventional method. Then, the leakage amount of alkali in the cleaning waste water can be significantly reduced, and the cleaning time can be significantly shortened.
The effect of the present invention is that by dispersing the acid throughout the ion exchange resin layer, the alkali remaining in the ion exchange resin particles or in the voids between the ion exchange resin particles instantly interacts with the added acid. Furthermore, if the ion exchange resin is an anion exchange resin, the sodium carboxylate produced by the reaction of equation (1) described above and the added acid (for example, hydrochloric acid)
reacts to form a carboxylic acid as shown in formula (4), or a salt-form exchange group generated by the reaction of an OH-form exchange group with the added acid and sodium carboxylate (5) This is thought to be due to the formation of carboxylic acid due to the diffusion reaction within the ion exchange particles as shown in the equation.
Ｒ−COONa＋HCl→Ｒ−COOH＋NaCl …(4)
Ｒ≡NHCl＋Ｒ−COONa＋H2O→Ｒ≡NHOH
＋Ｒ−COOH＋NaCl …(5)
いずれにしても本発明によりイオン交換樹脂を
アルカリ性溶液で処理した後の洗浄が短時間とな
り、再生用水量を低減させるとともに再生時間を
大幅に短縮することが可能となる。R-COONa+HCl→R-COOH+NaCl...(4) R≡NHCl+R-COONa+H 2 O→R≡NHOH+R-COOH+NaCl...(5) In any case, the present invention shortens the cleaning time after treating the ion exchange resin with an alkaline solution. This makes it possible to reduce the amount of water for regeneration and to significantly shorten the regeneration time.
以下に本発明の実施例を説明する。 Examples of the present invention will be described below.
実施例 １
ブドウ糖液の脱塩処理に使用した弱塩基性アニ
オン交換樹脂アンバーライト（登録商標、以下同
様）IRA−68（弱塩基性交換容量4.70ｍeq／ｇ−
dry resinカルボキシル交換容量0.89ｍeq／ｇ−
dry resin）１をカラムに入れ、1N−NaOH1.5
をSV4で通薬し、次いで純水を使用してSV4で
20分間押出した後、イオン交換樹脂層上部まで、
カラム内の水を抜き、2N−HClを75ml添加し、直
ちにカラム下部より空気を1N／minの割合で３
分間供給し、カラム内のイオン交換樹脂を充分に
混合した。その後、純水を使用してSV10で洗浄
した結果、第１図１に示すように洗浄廃水のPHが
8.0になるに要する時間は約12分であつた。Example 1 Weakly basic anion exchange resin Amberlite (registered trademark, hereinafter the same) used for desalting of glucose solution IRA-68 (weakly basic exchange capacity 4.70 meq/g-
dry resin carboxyl exchange capacity 0.89meq/g-
Put 1N-NaOH1.5 into the column.
SV4, then SV4 using pure water.
After extruding for 20 minutes, up to the top of the ion exchange resin layer,
Drain the water from the column, add 75ml of 2N-HCl, and immediately blow air from the bottom of the column at a rate of 1N/min.
The ion exchange resin in the column was thoroughly mixed. After that, as a result of washing with SV10 using pure water, the pH of the washing waste water was as shown in Figure 1.
It took about 12 minutes to reach 8.0.
比較例として、押出後、酸を添加しないで純水
を使用してSV10で洗浄した結果、第１図２に示
すように洗浄廃水のPHが8.0になるに要する時間
は47分であつた。また純水の代わりに鉱酸濃度が
50mgCaCO3／の酸性軟水を使用してSV10で洗
浄した結果、第１図３に示すように洗浄廃水のPH
が8.0になるに要する時間は41分であつた。 As a comparative example, as a result of washing with SV10 using pure water without adding acid after extrusion, the time required for the pH of the washing waste water to reach 8.0 was 47 minutes as shown in FIG. 1 and 2. Also, instead of pure water, mineral acid concentration
As a result of cleaning with SV10 using acidic soft water of 50mgCaCO 3 /, the pH of the cleaning wastewater was as shown in Figure 1.
It took 41 minutes to reach 8.0.
実施例 ２
強酸性カチオン交換樹脂アンバーライト200、
１をカラムに入れ、1N−Na2SO32をSV4で通
薬し、次いで純水を使用してSV4で20分間押出し
た後、イオン交換樹脂層上部まで、カラム内の水
を抜き、2N−HCl10mlを添加し、直ちにカラム下
部より空気を1N／minの割合で３分間供給し、
カラム内のイオン交換樹脂を充分に混合した。そ
の後純水を使用してSV10で洗浄した結果、第２
図１に示すように洗浄廃水の電気伝導率は急激に
低下し、５μＳ／cmat25℃になるに要する時間は
３分であつた。Example 2 Strongly acidic cation exchange resin Amberlite 200,
1 was put in a column, 1N-Na 2 SO 3 2 was passed through SV4, and then extruded for 20 minutes using SV4 using pure water. The water in the column was removed to the top of the ion exchange resin layer, and 2N -Add 10ml of HCl, immediately supply air from the bottom of the column at a rate of 1N/min for 3 minutes,
The ion exchange resin in the column was thoroughly mixed. After that, as a result of washing with SV10 using pure water, the second
As shown in FIG. 1, the electrical conductivity of the cleaning wastewater decreased rapidly, and it took 3 minutes to reach 5 μS/cmat at 25°C.
また空気混合しながら酸を添加したものも第２
図２に示すように非常に良好な洗浄性を示した。 Also, the second type is one in which acid is added while mixing with air.
As shown in FIG. 2, very good cleaning performance was exhibited.
比較例として、酸を添加しないで純水を使用し
てSV10で洗浄した結果、第２図３に示すように
洗浄性が悪く８μＳ／cmになるのに29分を要し
た。 As a comparative example, as a result of cleaning with SV10 using pure water without adding acid, the cleaning performance was poor as shown in FIG. 2, and it took 29 minutes to reach 8 μS/cm.
実施例 ３
強酸性カチオン交換樹脂アンバーライトIR−
120B、１をカラムに入れ、1N−NaOH2を
SV4で通薬し、次いで純水を使用してSV4で20分
間押出した後、イオン交換樹脂層上部までカラム
内の水を抜き、2N−HClを15ml添加し、直ちにカ
ラム下部より空気を1N／minの割合で３分間供
給しカラム内のイオン交換樹脂を充分に混合し
た。その後純水を使用してSV10で洗浄した結
果、第３図１に示すように洗浄廃水の電気伝導率
が５μＳ／cmat25℃に達するに要する時間は約２
分であつた。Example 3 Strongly acidic cation exchange resin Amberlite IR-
Put 120B, 1 into the column and add 1N-NaOH2.
After extruding with SV4 for 20 minutes using pure water, drain the water in the column to the top of the ion-exchange resin layer, add 15ml of 2N-HCl, and immediately pump air 1N/1 from the bottom of the column. The ion exchange resin in the column was sufficiently mixed by supplying at a rate of min for 3 minutes. After that, as a result of washing at SV10 using pure water, as shown in Figure 3, the time required for the electrical conductivity of the washing waste water to reach 5μS/cmat25℃ is approximately 2
It was hot in minutes.
比較例として、酸を添加しないで、純水を使用
してSV10で洗浄した結果、第３図２に示すよう
に洗浄性が悪く、洗浄廃水の電気伝導率が8.5μ
Ｓ／cmat25℃に達するに要する時間が22分であつ
た。 As a comparative example, as a result of cleaning with SV10 using pure water without adding acid, the cleaning performance was poor as shown in Figure 3 2, and the electrical conductivity of the cleaning waste water was 8.5μ.
The time required to reach S/cmat 25°C was 22 minutes.
図面はいずれも実施例における洗浄効果を示す
グラフであり、第１図は実施例１におけるアニオ
ン交換樹脂の洗浄効果を示すものであつて、縦軸
に洗浄廃水のPH、横軸に洗浄時間を示し、第１図
中、曲線１は本発明の洗浄方法、曲線２および３
は従来の洗浄方法の結果である。また第２図およ
び第３図は実施例２および３におけるカチオン交
換樹脂の洗浄効果を示すものであつて、縦軸に洗
浄廃水の電気伝導率、横軸に洗浄時間を示し、第
２図中、曲線１および２は本発明の洗浄方法、曲
線３は従来の洗浄方法の結果であり、第３図、中
曲線１は本発明の洗浄方法、曲線２は従来の洗浄
方法である。
The drawings are all graphs showing the cleaning effect in Examples, and Figure 1 shows the cleaning effect of the anion exchange resin in Example 1, with the vertical axis representing the pH of the cleaning wastewater and the horizontal axis representing the cleaning time. In FIG. 1, curve 1 represents the cleaning method of the present invention, curves 2 and 3
is the result of conventional cleaning methods. Furthermore, FIGS. 2 and 3 show the cleaning effects of the cation exchange resins in Examples 2 and 3. The vertical axis shows the electrical conductivity of the cleaning wastewater, and the horizontal axis shows the cleaning time. , curves 1 and 2 are the results of the cleaning method of the present invention, and curve 3 is the result of the conventional cleaning method. In FIG. 3, middle curve 1 is the result of the cleaning method of the present invention, and curve 2 is the result of the conventional cleaning method.
Claims (1)
後に洗浄するにあたり、イオン交換樹脂層のアル
カリ性溶液を押出水で置換した後、当該イオン交
換樹脂層に小量の酸を添加した直後にイオン交換
樹脂層を混合するか、あるいは当該イオン交換樹
脂層に小量の酸を添加しながらイオン交換樹脂層
を混合し、その後に洗浄水でイオン交換樹脂層を
洗浄することを特徴とするイオン交換樹脂の洗浄
方法。1 When cleaning the ion exchange resin after treating it with an alkaline solution, replace the alkaline solution in the ion exchange resin layer with extrusion water, and immediately after adding a small amount of acid to the ion exchange resin layer, remove the ion exchange resin layer. A method for cleaning an ion exchange resin, characterized by mixing the ion exchange resin layer, or mixing the ion exchange resin layer while adding a small amount of acid to the ion exchange resin layer, and then cleaning the ion exchange resin layer with cleaning water. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7717680A JPS5724646A (en) | 1980-06-10 | 1980-06-10 | Washing method for ion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7717680A JPS5724646A (en) | 1980-06-10 | 1980-06-10 | Washing method for ion exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5724646A JPS5724646A (en) | 1982-02-09 |
| JPS6260943B2 true JPS6260943B2 (en) | 1987-12-18 |
Family
ID=13626483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7717680A Granted JPS5724646A (en) | 1980-06-10 | 1980-06-10 | Washing method for ion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5724646A (en) |
-
1980
- 1980-06-10 JP JP7717680A patent/JPS5724646A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5724646A (en) | 1982-02-09 |
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