JP2002138382A - Method for treating collected ash in digesting chemical recovery process - Google Patents
Method for treating collected ash in digesting chemical recovery processInfo
- Publication number
- JP2002138382A JP2002138382A JP2000332918A JP2000332918A JP2002138382A JP 2002138382 A JP2002138382 A JP 2002138382A JP 2000332918 A JP2000332918 A JP 2000332918A JP 2000332918 A JP2000332918 A JP 2000332918A JP 2002138382 A JP2002138382 A JP 2002138382A
- Authority
- JP
- Japan
- Prior art keywords
- ion
- exchange resin
- solution
- collected ash
- ion exchange
- 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.)
- Granted
Links
- 238000011084 recovery Methods 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 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 abstract description 39
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 32
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 7
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010411 cooking Methods 0.000 claims description 22
- 238000005342 ion exchange Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 abstract description 11
- 239000000460 chlorine Substances 0.000 abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011591 potassium Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 241000270295 Serpentes Species 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005341 cation exchange Methods 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical class CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- NMGSERJNPJZFFC-UHFFFAOYSA-N carbonic acid;sulfuric acid Chemical compound OC(O)=O.OS(O)(=O)=O NMGSERJNPJZFFC-UHFFFAOYSA-N 0.000 description 1
- 238000009993 causticizing Methods 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、蒸解薬品回収工程
の捕集灰（ダスト）の処理方法に関し、詳しくは、パル
プの製造における蒸解薬品回収工程の捕集灰に含まれる
塩素分およびカリウム分を除去するための捕集灰の処理
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating collected ash (dust) in a cooking chemical recovery step, and more particularly, to a chlorine content and a potassium content contained in the collection ash in the cooking chemical recovery step in pulp production. The present invention relates to a method for treating collected ash for removing ash.
【０００２】[0002]
【従来の技術】例えばクラフトパルプの製造において
は、苛性ソーダと硫化ソーダの約７対３の混合液を使用
して原料チップを蒸解する。この蒸解工程においては、
苛性ソーダと硫化ソーダは、それぞれ、不活性な炭酸ソ
ーダと硫酸ソーダに変化する。そして、パルプは、種々
の精製工程および漂白工程を経て製品となる。一方、パ
ルプから分離された蒸解廃液（黒液）は、濃縮後に蒸解
薬品回収工程（ソーダ回収ポイラー）で燃焼処理され
る。その結果、硫酸ソーダは還元されて硫化ソーダに変
換される。また、炭酸ソーダは、その後の苛性化工程で
生石灰により還元されて苛性ソーダに変換される。上記
の再生された硫化ソーダや苛性ソーダは水に溶解して回
収され、これらにより蒸解液（白液）が調製される。2. Description of the Related Art In the production of kraft pulp, for example, a raw material chip is digested using a mixture of caustic soda and sodium sulfide of about 7: 3. In this cooking process,
Caustic soda and sodium sulfide are converted to inert sodium carbonate and sodium sulfate, respectively. And pulp becomes a product through various refining processes and bleaching processes. On the other hand, the cooking effluent (black liquor) separated from the pulp is burned in a cooking chemical recovery step (soda recovery boiler) after concentration. As a result, the sodium sulfate is reduced and converted to sodium sulfide. Further, sodium carbonate is reduced by quick lime in a subsequent causticizing step and is converted into caustic soda. The regenerated sodium sulfide and caustic soda are dissolved and recovered in water, and a cooking liquor (white liquor) is prepared by these.
【０００３】蒸解薬品は上記の様に回収されて再使用さ
れるが、木材などから混入して蓄積された塩素分および
カリウム分（不純物）により回収ポイラーが腐食すると
いう問題がある。従って、蒸解薬品回収工程の捕集灰か
ら塩素分およびカリウム分を除去する必要がある。[0003] Cooking chemicals are recovered and reused as described above, but there is a problem in that the recovery boiler is corroded by chlorine and potassium (impurities) accumulated from wood and the like. Therefore, it is necessary to remove chlorine and potassium from the collected ash in the cooking chemical recovery step.
【０００４】特開平９−２９２０１号公報には、「ソー
ダ回収ボイラーの捕集灰からの食塩及びカリウム塩の除
去方法」が提案されている。そこには、捕集灰の組成
（重量％）の一例として、ＮａＣｌ：９．７％、Ｎａ2
ＳＯ4：６７．２％、Ｎａ2ＣＯ3：１０．１％、ＫＣ
ｌ：１．５％、Ｋ2ＳＯ4：９．９％、Ｋ2ＣＯ3：１．６
％が示されている。斯かる捕集灰の水スラリーは、Ｎａ
2ＣＯ3の存在により強いアルカリ性である（通常１０以
上）。Japanese Unexamined Patent Publication No. 9-29201 proposes a "method of removing salt and potassium salt from collected ash of a soda recovery boiler". There, as an example of the composition (% by weight) of the collected ash, NaCl: 9.7%, Na 2
SO 4 : 67.2%, Na 2 CO 3 : 10.1%, KC
l: 1.5%, K 2 SO 4: 9.9%, K 2 CO 3: 1.6
%It is shown. The water slurry of such collected ash is Na
Strongly alkaline due to the presence of 2 CO 3 (usually 10 or more).
【０００５】特開平９−２９２０１号公報に記載の方法
は、上記の様な捕集灰の水スラリーのｐＨを硫酸添加に
より１０以下に、温度を２０℃以上に調整し、一定時間
保持して捕集灰中の食塩及びカリウム塩を水に溶解さ
せ、当該スラリーを２０℃未満の温度に冷却して固形分
を析出させた後、固形分と液体とに分離して液体は系外
に廃棄し、固形分は濃縮前の黒液に再溶解させ、その黒
液を黒液濃縮器の前流に戻すことによって固形分を回収
する方法である。In the method described in Japanese Patent Application Laid-Open No. 9-29201, the pH of the collected ash water slurry is adjusted to 10 or less by adding sulfuric acid, the temperature is adjusted to 20 ° C. or more, and the temperature is maintained for a certain period of time. The salt and potassium salt in the collected ash are dissolved in water, and the slurry is cooled to a temperature of less than 20 ° C. to precipitate a solid, then separated into a solid and a liquid, and the liquid is disposed of outside the system. In this method, the solid content is redissolved in black liquor before concentration, and the black liquor is returned to the upstream of the black liquor concentrator to recover the solid content.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、パル
プの製造における蒸解薬品回収工程の捕集灰から塩素分
およびカリウム分を除去するための捕集灰の処理方法を
提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for treating collected ash for removing chlorine and potassium from collected ash in a cooking chemical recovery step in pulp production. .
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明の要旨
は、両性イオン交換樹脂の充填床に蒸解薬品回収工程の
捕集灰の溶解液と水とを交互に通液し、硫酸イオン及び
炭酸イオンに富む画分と塩素イオンに富む画分とに分離
して回収する塩素イオン分離工程と、カチオン交換樹脂
の充填床に上記の捕集灰の溶解液または塩素イオン分離
工程で回収された硫酸イオン及び炭酸イオンに富む画分
の溶液を通液するカリウムイオン吸着除去工程とを包含
することを特徴とする蒸解薬品回収工程の捕集灰の処理
方法に存する。That is, the gist of the present invention is that a solution of trapped ash in a cooking chemical recovery step and water are alternately passed through a packed bed of amphoteric ion exchange resin to form sulfate ion and carbonate. A chloride ion separation step of separating and recovering into an ion-rich fraction and a chloride ion-rich fraction, and a solution of the collected ash or sulfuric acid recovered in the chloride ion separation step on a packed bed of a cation exchange resin. And a step of adsorbing and removing potassium ions by passing a solution of a fraction rich in ions and carbonate ions.
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明は各種のパルプの製造における蒸解薬品回収工程
の捕集灰に適用することが出来る。パルプの例として
は、クラフトパルプ、セミケミカルパルプ、ケミグラン
ドパルプ、サルファイトパルプ等のナトリウムべース蒸
解工程を経て得られる各種のパルプが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
INDUSTRIAL APPLICABILITY The present invention can be applied to collected ash in a cooking chemical recovery step in the production of various pulp. Examples of the pulp include various pulp obtained through a sodium-based cooking step such as kraft pulp, semi-chemical pulp, chemi-grand pulp, and sulfite pulp.
【０００９】蒸解薬品回収工程においては、蒸解廃液
（黒液）を濃縮した後に回収ボイラーで燃焼する。その
際、発生する灰はミストコットレル等の電気集塵機で捕
集される。本発明は、斯かる捕集灰に含まれる塩素分お
よびカリウム分を除去する。具体的には、両性イオン交
換樹脂の充填床に蒸解薬品回収工程の捕集灰の溶解液と
水とを交互に通液し、硫酸イオン及び炭酸イオンに富む
画分と塩素イオンに富む画分とに分離して回収する塩素
イオン分離工程と、カチオン交換樹脂の充填床に上記の
捕集灰の溶解液または塩素イオン分離工程で回収された
硫酸イオン及び炭酸イオンに富む画分の溶液を通液する
カリウムイオン吸着除去工程とを行う。In the cooking chemical recovery step, the cooking waste liquor (black liquor) is concentrated and then burned in a recovery boiler. At that time, the generated ash is collected by an electric precipitator such as a mist cotter. The present invention removes chlorine and potassium contained in such collected ash. Specifically, a solution and a water solution of the collected ash in the cooking chemical recovery step are alternately passed through a packed bed of amphoteric ion exchange resin, and a fraction rich in sulfate and carbonate ions and a fraction rich in chloride ions And a solution of the above-mentioned ash solution or a fraction rich in sulfate and carbonate ions collected in the chloride ion separation step through a packed bed of cation exchange resin. And a step of removing and absorbing potassium ions.
【００１０】捕集灰の溶解には、電気集塵機に付設され
た湿式スクラバーから得られた灰回収液を使用すること
が出来る。また、通常、溶解液は、溶解槽の後に配置さ
れた沈殿槽と濾過器とで処理された後にイオン交換樹脂
で処理される。通常、捕集灰に対して３〜１０重量倍の
水が使用される。For dissolving the collected ash, an ash recovered liquid obtained from a wet scrubber attached to an electric dust collector can be used. Usually, the solution is treated with an ion exchange resin after being treated in a settling tank and a filter arranged after the dissolving tank. Usually, 3 to 10 times by weight of water is used for the collected ash.
【００１１】前記の塩素イオン分離工程とカリウムイオ
ン吸着除去工程とは、何れを先行させてもよいが、本発
明の好ましい態様においては、塩素イオン分離工程はカ
リウムイオン吸着除去工程より先行して行われる。[0011] Either of the chlorine ion separation step and the potassium ion adsorption and removal step may precede, but in a preferred embodiment of the present invention, the chloride ion separation step is performed prior to the potassium ion adsorption and removal step. Will be
【００１２】塩素イオン分離工程で使用する両性イオン
交換樹脂としては、特に制限されず、従来公知の樹脂を
使用することが出来る。両性イオン交換樹脂は、イオン
・リターデションを利用する分離における分離剤として
知られている。すなわち、両性イオン交換樹脂は、同一
樹脂内の陽イオン交換基と陰イオン交換基とによって内
部塩を形成し、イオン排除とは反対に電解質を非電解質
よりも強く吸着する性質を有し、電解質と非電解質（例
えば食塩と糖）とを分離し得る性質を有する。そして、
水で溶離展開を行うと、電解質は、吸着力が強いために
非電解質よりも遅れて溶離される（イオン・リターデシ
ョン）。The amphoteric ion exchange resin used in the chlorine ion separation step is not particularly limited, and a conventionally known resin can be used. Amphoteric ion exchange resins are known as separating agents in separations utilizing ion retardation. That is, an amphoteric ion exchange resin forms an internal salt with a cation exchange group and an anion exchange group in the same resin, and has a property of adsorbing an electrolyte more strongly than a non-electrolyte, as opposed to ion exclusion. And a non-electrolyte (eg, salt and sugar). And
When elution is carried out with water, the electrolyte is eluted later than the non-electrolyte due to its strong adsorption power (ion retardation).
【００１３】ところが、両性イオン交換樹脂によって捕
集灰の溶解液を処理した場合、硫酸イオン及び炭酸イオ
ンに富む画分と塩素イオンに富む画分とに分離される。
すなわち、塩素イオンは両性イオン交換樹脂に強く吸着
され、水によって溶離させることが出来る。本発明は、
上記の様な硫酸イオン及び炭酸イオンと塩素イオンとの
間の顕著な選択性を利用し、捕集灰の溶解液から塩素イ
オンを分離する。However, when the solution of the collected ash is treated with an amphoteric ion exchange resin, it is separated into a fraction rich in sulfate and carbonate ions and a fraction rich in chloride ions.
That is, chloride ions are strongly adsorbed by the amphoteric ion exchange resin and can be eluted by water. The present invention
By utilizing the remarkable selectivity between sulfate ion and carbonate ion and chloride ion as described above, chloride ion is separated from the solution of the collected ash.
【００１４】本発明において、両性イオン交換樹脂とし
ては、以下の式（１）で表されるイオン交換基を有する
イオン交換樹脂が好適に使用される。In the present invention, as the amphoteric ion exchange resin, an ion exchange resin having an ion exchange group represented by the following formula (1) is preferably used.
【００１５】[0015]
【化２】 Embedded image
【００１６】上記の式（１）において、Ｒ1及びＲ2は各
々メチル基、ｍ及びｎは各々１の整数であることが好ま
しい。斯かるイオン交換樹脂は、例えば、スチレンとジ
ビニルベンゼンとの共重合体の様な芳香族架橋共重合体
の芳香核に上記のイオン交換基を直接結合したグリシン
型両性イオン交換樹脂として公知であり、「ダイヤイオ
ン（登録商標）ＡＭＰ０１」（三菱化学社製品）として
市販されている。斯かるグリシン型両性イオン交換樹脂
は、ハロメチル基を有する芳香族架橋共重合体とＮ，Ｎ
−ジメチルグリシン誘導体とを反応させた後に加水分解
することによって得られる。In the above formula (1), R 1 and R 2 are each preferably a methyl group, and m and n are each preferably an integer of 1. Such an ion exchange resin is known as, for example, a glycine-type amphoteric ion exchange resin in which the above ion exchange group is directly bonded to an aromatic nucleus of an aromatic crosslinked copolymer such as a copolymer of styrene and divinylbenzene. And "Diaion (registered trademark) AMP01" (product of Mitsubishi Chemical Corporation). Such a glycine-type amphoteric ion exchange resin comprises an aromatic cross-linked copolymer having a halomethyl group and N, N
-Obtained by reacting with a dimethylglycine derivative followed by hydrolysis.
【００１７】また、両性イオン交換樹脂は、例えば、三
次元構造の陰イオン交換樹脂に酸性基を持った単量体
（例えばアクリル酸）と重合開始剤とを吸収させて陰イ
オン交換樹脂の三次元構造の内部で重合させることによ
っても得ることが出来る。斯かる方法で得られる両性イ
オン交換樹脂はスネークケージ型両性イオン交換樹脂と
呼ばれ、次の様な構造的特徴を備えている。例えば、上
記の例の場合は、陰イオン交換樹脂樹脂の三次元構造の
中に陽イオン交換基がヘビの様に絡まった状態で結合し
ている。従って、陽イオン交換基と陰イオン交換基とが
独立して別々に存在する。The amphoteric ion exchange resin is, for example, a three-dimensional anion exchange resin which absorbs a monomer having an acidic group (for example, acrylic acid) and a polymerization initiator to form a tertiary anion exchange resin. It can also be obtained by polymerizing inside the original structure. The amphoteric ion exchange resin obtained by such a method is called a snake cage type amphoteric ion exchange resin and has the following structural features. For example, in the case of the above example, a cation exchange group is bound in a three-dimensional structure of the anion exchange resin in a state of being entangled like a snake. Therefore, a cation exchange group and an anion exchange group are present independently and separately.
【００１８】前記のグリシン型両性イオン交換樹脂は、
上記の様なスネークケージ型両性イオン交換樹脂と異な
り、前記の式（１）で表される様に１種のイオン交換基
が陽性部と陰性部とを有している。そのため、次の様な
効果を有する。The glycine-type amphoteric ion exchange resin is
Unlike the snake cage type amphoteric ion exchange resin as described above, one type of ion exchange group has a positive portion and a negative portion as represented by the above formula (1). Therefore, the following effects are obtained.
【００１９】すなわち、捕集灰の溶解液は強アルカリ性
であるため、陽イオン交換基と陰イオン交換基とが独立
して別々に存在するスネークケージ型両性イオン交換樹
脂を使用した場合は、スネークケージを形成するイオン
交換基の脱離などの耐薬品性の問題が懸念されるが、前
記のグリシン型両性イオン交換樹脂は優れた耐薬品性を
有する。That is, since the solution of the collected ash is strongly alkaline, when a snake cage type amphoteric ion exchange resin in which a cation exchange group and an anion exchange group are present independently and separately is used, the snake is difficult. Although there is a concern about the problem of chemical resistance such as elimination of ion-exchange groups forming the cage, the glycine-type amphoteric ion exchange resin has excellent chemical resistance.
【００２０】塩素イオン分離工程においては、両性イオ
ン交換樹脂の充填床に蒸解薬品回収工程の捕集灰の溶解
液と水とを交互に通液し、硫酸イオン及び炭酸イオンに
富む画分と塩素イオンに富む画分とに分離して回収す
る。イオン交換樹脂の充填床の形成には通常のイオン交
換塔が使用される。通液する際の空間速度（ＳＶ）は、
通常１〜１０ｈｒ-1とされ、温度は、８０℃以下であれ
ば特に問題はなく、通常２０〜６０℃とされる。In the chlorine ion separation step, a solution of the collected ash and water in the cooking chemical recovery step are alternately passed through a packed bed of an amphoteric ion exchange resin to form a fraction rich in sulfate ions and carbonate ions and chlorine. It is separated and collected into an ion-rich fraction. An ordinary ion exchange column is used for forming a packed bed of the ion exchange resin. The space velocity (SV) when passing the liquid is
The temperature is usually 1 to 10 hr -1, and there is no particular problem if the temperature is 80 ° C. or less, and the temperature is usually 20 to 60 ° C.
【００２１】塩素イオン分離工程においては、先ず、捕
集灰の溶解液を通液する。これにより、硫酸イオン及び
炭酸イオンに富む画分（塩素イオンが実質的に含有され
ていない溶液）が回収される。斯かる通液の継続によ
り、やがて、塩素イオンの漏出が始まる。この時点で捕
集灰の溶解液の通液を停止する。次に、溶離液として水
を通液する。これにより、塩素イオンに富む画分が回収
されてグリシン型両性イオン交換樹脂の再生が行われ
る。上記の操作を繰り返して行うことにより、連続し
て、捕集灰の溶解液を硫酸イオン及び炭酸イオンに富む
画分と塩素イオンに富む画分とに分離して回収すること
が出来る。In the chlorine ion separation step, first, a solution of the collected ash is passed. Thus, a fraction rich in sulfate ions and carbonate ions (a solution substantially free of chloride ions) is recovered. With the continuation of the flow, the leakage of chlorine ions starts. At this point, the flow of the solution of the collected ash is stopped. Next, water is passed as an eluent. Thereby, the fraction rich in chloride ions is recovered, and the glycine-type amphoteric ion exchange resin is regenerated. By repeatedly performing the above operation, the solution of the collected ash can be continuously separated and collected into a fraction rich in sulfate ions and carbonate ions and a fraction rich in chloride ions.
【００２２】一方、カリウムイオン吸着除去工程におい
て使用するカチオン交換樹脂としては、特に制限され
ず、市販の樹脂から適宜選択することが出来る。例え
ば、Ｎａ型強酸性イオン交換樹脂（三菱化学社製「ダイ
ヤイオン（登録商標）ＳＫ１１０」）は好適なカチオン
交換樹脂の一例である。On the other hand, the cation exchange resin used in the potassium ion adsorption removal step is not particularly limited, and can be appropriately selected from commercially available resins. For example, a Na-type strongly acidic ion exchange resin (“Diaion (registered trademark) SK110” manufactured by Mitsubishi Chemical Corporation) is an example of a suitable cation exchange resin.
【００２３】カチオン交換樹脂の充填床の形成には前記
と同様に通常のイオン交換塔が使用される。また、捕集
灰の溶解液または塩素イオン分離工程で回収された硫酸
イオン及び炭酸イオンに富む画分の溶液を通液する際の
何れの場合も、通液する際の空間速度（ＳＶ）は、通常
１〜１０ｈｒ-1とされ、温度は、８０℃以下であれば特
に問題はなく、通常２０〜６０℃とされる。斯かる通液
の継続により、やがて、カリウムイオンの漏出が始ま
る。この時点で上記の通液を停止する。次に、再生剤と
して食塩水を通液する。これにより、カリウムを吸着し
た強酸性イオン交換樹脂のＮａ型への再生が行われる。
上記の操作を繰り返して行うことにより、連続して、カ
リウムイオンを吸着除去することが出来る。なお、上記
の再生は、酸（例えば硫酸水溶液）を通液した後に苛性
ソーダ水溶液または食塩水を通液する方法によってもよ
い。For forming the packed bed of the cation exchange resin, a usual ion exchange column is used in the same manner as described above. In addition, in any case of passing the solution of the collected ash or the solution of the fraction rich in sulfate ions and carbonate ions recovered in the chloride ion separation step, the space velocity (SV) when passing the solution is as follows: The temperature is usually 1 to 10 hr -1, and the temperature is not particularly limited as long as it is 80 ° C. or lower, and is usually 20 to 60 ° C. With the continuation of the passage, the leakage of potassium ions starts. At this point, the above-mentioned liquid passing is stopped. Next, a saline solution is passed as a regenerating agent. Thereby, the regeneration of the strongly acidic ion exchange resin adsorbing potassium to the Na type is performed.
By repeatedly performing the above operation, potassium ions can be continuously removed by adsorption. The regeneration may be performed by passing an acid (for example, an aqueous sulfuric acid solution) and then passing an aqueous caustic soda solution or a saline solution.
【００２４】上記の様にして塩素分およびカリウム分の
除去された硫酸イオン及び炭酸イオンに富む画分は、蒸
解液（白液）の調製に再使用される。The sulfate- and carbonate-rich fraction from which the chlorine and potassium components have been removed as described above is reused for preparing a cooking liquor (white liquor).
【００２５】[0025]
【実施例】以下、本発明を実施例により更に詳細に説明
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 in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.
【００２６】実施例１ クラフトパルプの製造における蒸解薬品回収工程（ソー
ダ回収ポイラー）の捕集灰を５０℃で４０ｗ／ｖ％の条
件で純水に溶解し、０．４５μｍメンブレンフィルター
で濾過処理し、表１に示す組成を有する濾液（原液）を
得た。Example 1 The ash collected in the cooking chemical recovery step (soda recovery boiler) in the production of kraft pulp was dissolved in pure water at 50 ° C. under the condition of 40 w / v%, and filtered through a 0.45 μm membrane filter. A filtrate (stock solution) having the composition shown in Table 1 was obtained.
【００２７】[0027]
【表１】 [Table 1]
【００２８】グリシン型両性イオン交換樹脂［ダイヤイ
オン（登録商標）ＡＭＰ０１］７８０ｍＬを充填した内
径３０ｍｍの可動栓付ガラス製カラムに、温度６０℃に
保温した原液を空間速度（ＳＶ）４．０ｈ-1で２３４ｍ
Ｌ通液し、続いて、温度６０℃に保温した純水を空間速
度（ＳＶ）４．０ｈ-1で７６６ｍＬ通液した。カラム流
出液の各成分は図１の様であった。その際、カラム流出
液を硫酸イオン及び炭酸イオンに富む回収画分と不純物
である塩素イオンに富む排水画分に分画した。回収画分
（図１中のＡ）における各成分回収率および排水画分へ
の各成分除去率は表２の様であった。A stock solution kept at a temperature of 60 ° C. was placed in a glass column with a movable stopper having a 30 mm inner diameter and filled with 780 mL of a glycine-type amphoteric ion exchange resin [Diaion (registered trademark) AMP01] at a space velocity (SV) of 4.0 h − 234m for 1
Then, 766 mL of pure water kept at a temperature of 60 ° C. was passed at a space velocity (SV) of 4.0 h −1 . Each component of the column effluent was as shown in FIG. At that time, the column effluent was fractionated into a recovered fraction rich in sulfate ions and carbonate ions and a wastewater fraction rich in chloride ions as impurities. Table 2 shows the respective component recovery rates in the recovered fraction (A in FIG. 1) and the respective component removal rates in the wastewater fraction.
【００２９】[0029]
【表２】 [Table 2]
【００３０】次いで、Ｎａ型強酸性イオン交換樹脂［ダ
イヤイオン（登録商標）ＳＫ１１０］３００ｍＬを充填
した内径２２ｍｍのガラス製カラムに、上記で得られた
硫酸イオン及び炭酸イオンに富む回収画分６００ｍＬを
空間速度（ＳＶ）１．０ｈ-1で通液した。カラム流出液
のＮａ及びＫは図２のようであり、回収画分（図２中の
Ｂ）におけるＮａ及びＫ濃度ならびにＫ除去率は表３の
様であった。Next, 600 mL of the recovered fraction rich in sulfate and carbonate ions obtained above was placed in a glass column having an inner diameter of 22 mm packed with 300 mL of Na type strongly acidic ion exchange resin [Diaion (registered trademark) SK110]. The solution was passed at a space velocity (SV) of 1.0 h -1 . The Na and K in the column effluent were as shown in FIG. 2, and the Na and K concentrations and the K removal ratio in the recovered fraction (B in FIG. 2) were as shown in Table 3.
【００３１】[0031]
【表３】 [Table 3]
【００３２】上記の実施例から明らかな様に、両性イオ
ン交換樹脂および強酸性イオン交換樹脂により、クラフ
トパルプの製造における蒸解薬品回収工程（ソーダ回収
ポイラー）の捕集灰に含まれる塩素分およびカリウム分
の除去が可能であることが確認された。As is evident from the above examples, the chlorine and potassium contained in the collected ash in the cooking chemical recovery step (soda recovery boiler) in the production of kraft pulp by the amphoteric ion exchange resin and the strongly acidic ion exchange resin. Has been confirmed to be possible.
【００３３】[0033]
【発明の効果】以上説明した本発明によれば、パルプの
製造における蒸解薬品回収工程の捕集灰から塩素分およ
びカリウム分を除去するための捕集灰の処理方法が提供
され、本発明の工業的価値は顕著である。According to the present invention described above, a method for treating collected ash for removing chlorine and potassium from collected ash in the cooking chemical recovery step in pulp production is provided. The industrial value is significant.
【図１】実施例１の塩素イオン分離工程で得られたカラ
ム流出液の各成分の流出状態の一例を示す流出曲線FIG. 1 is an outflow curve showing an example of an outflow state of each component of a column effluent obtained in a chloride ion separation step in Example 1.
【図２】実施例１のカリウムイオン吸着除去工程で得ら
れたカラム流出液の各成分の流出状態の一例を示す流出
曲線FIG. 2 is an outflow curve showing an example of the outflow state of each component of a column effluent obtained in the potassium ion adsorption removal step of Example 1.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小貫 政将 神奈川県横浜市青葉区鴨志田町1000番地 日本錬水株式会社研究所内 (72)発明者 古荘 三郎 東京都豊島区南大塚三丁目43番11号 日本 錬水株式会社内 Ｆターム(参考） 4D004 AA36 AB03 AB06 AC05 BA06 CA34 CA40 CA47 CB05 CC03 CC15 4L055 BC14 FA30 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masamasa Onuki 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside the Japan Refined Water Research Laboratory (72) Inventor Saburo Furuso 3-43-11 Minamiotsuka, Toshima-ku, Tokyo No. Japan Rensui Co., Ltd. F-term (reference) 4D004 AA36 AB03 AB06 AC05 BA06 CA34 CA40 CA47 CB05 CC03 CC15 4L055 BC14 FA30
Claims (3)
回収工程の捕集灰の溶解液と水とを交互に通液し、硫酸
イオン及び炭酸イオンに富む画分と塩素イオンに富む画
分とに分離して回収する塩素イオン分離工程と、カチオ
ン交換樹脂の充填床に上記の捕集灰の溶解液または塩素
イオン分離工程で回収された硫酸イオン及び炭酸イオン
に富む画分の溶液を通液するカリウムイオン吸着除去工
程とを包含することを特徴とする蒸解薬品回収工程の捕
集灰の処理方法。1. A solution enriched in sulfated and carbonated ions and a fraction rich in chloride ions, wherein a solution of the collected ash from the cooking chemical recovery step and water are alternately passed through a packed bed of amphoteric ion exchange resin. And a solution of the above collected ash solution or a fraction rich in sulfate ions and carbonate ions recovered in the chloride ion separation step, through a packed bed of cation exchange resin. A process for collecting ash in a cooking chemical recovery step, which comprises a step of removing and absorbing potassium ions.
着除去工程より先行して行われる請求項１に記載の処理
方法。2. The treatment method according to claim 1, wherein the chlorine ion separation step is performed prior to the potassium ion adsorption removal step.
ン交換樹脂が以下の式（１）で表されるイオン交換基を
有するイオン交換樹脂である請求項１又は２に記載の処
理方法。 【化１】 3. The treatment method according to claim 1, wherein the amphoteric ion exchange resin used in the chlorine ion separation step is an ion exchange resin having an ion exchange group represented by the following formula (1). Embedded image
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004042140A1 (en) | 2002-11-05 | 2004-05-21 | Nippon Rensui Co. | Process for producing kraft pulp |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5440279A (en) * | 1977-09-05 | 1979-03-29 | Mitsubishi Paper Mills Ltd | Treating method for waste solution from pulp digestion |
| JPH0252090A (en) * | 1988-08-12 | 1990-02-21 | Shimizu Corp | Method and apparatus for making health drinking water by electrolysis and ion exchange |
| JPH0665884A (en) * | 1992-08-21 | 1994-03-08 | Daio Paper Corp | Production of acid and alkali |
| JPH0871553A (en) * | 1994-09-08 | 1996-03-19 | Nippon Rensui Kk | Method for separating chlorate from aqueous solution of alkali metal chloride |
| JP2001508838A (en) * | 1997-01-24 | 2001-07-03 | パルプ アンド ペーパー リサーチ インスチチュート オブ カナダ | Method for separating sulfide from pulping liquid using amphoteric resin |
| JP2002138381A (en) * | 2000-10-31 | 2002-05-14 | Nippon Rensui Co Ltd | Method for treating collected ash in digesting chemical recovery process |
-
2000
- 2000-10-31 JP JP2000332918A patent/JP4617561B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5440279A (en) * | 1977-09-05 | 1979-03-29 | Mitsubishi Paper Mills Ltd | Treating method for waste solution from pulp digestion |
| JPH0252090A (en) * | 1988-08-12 | 1990-02-21 | Shimizu Corp | Method and apparatus for making health drinking water by electrolysis and ion exchange |
| JPH0665884A (en) * | 1992-08-21 | 1994-03-08 | Daio Paper Corp | Production of acid and alkali |
| JPH0871553A (en) * | 1994-09-08 | 1996-03-19 | Nippon Rensui Kk | Method for separating chlorate from aqueous solution of alkali metal chloride |
| JP2001508838A (en) * | 1997-01-24 | 2001-07-03 | パルプ アンド ペーパー リサーチ インスチチュート オブ カナダ | Method for separating sulfide from pulping liquid using amphoteric resin |
| JP2002138381A (en) * | 2000-10-31 | 2002-05-14 | Nippon Rensui Co Ltd | Method for treating collected ash in digesting chemical recovery process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004042140A1 (en) | 2002-11-05 | 2004-05-21 | Nippon Rensui Co. | Process for producing kraft pulp |
| US7553394B2 (en) | 2002-11-05 | 2009-06-30 | Nippon Rensui Co. | Method for removing potassium from ash produced in a kraft pulping process recovery boiler using a Na-type cation exchange organic resin |
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| JP4617561B2 (en) | 2011-01-26 |
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