JPH072213B2 - Decolorization method of melanoidin coloring liquid - Google Patents
Decolorization method of melanoidin coloring liquidInfo
- Publication number
- JPH072213B2 JPH072213B2 JP61302780A JP30278086A JPH072213B2 JP H072213 B2 JPH072213 B2 JP H072213B2 JP 61302780 A JP61302780 A JP 61302780A JP 30278086 A JP30278086 A JP 30278086A JP H072213 B2 JPH072213 B2 JP H072213B2
- Authority
- JP
- Japan
- Prior art keywords
- acf
- melanoidin
- regeneration
- solution
- weight
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 20
- 238000004040 coloring Methods 0.000 title claims description 16
- 239000007788 liquid Substances 0.000 title description 21
- 238000004042 decolorization Methods 0.000 title description 20
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 description 37
- 230000008929 regeneration Effects 0.000 description 35
- 238000011084 recovery Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 8
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 235000013923 monosodium glutamate Nutrition 0.000 description 2
- 235000019992 sake Nutrition 0.000 description 2
- 229940073490 sodium glutamate Drugs 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Coloring Foods And Improving Nutritive Qualities (AREA)
- General Preparation And Processing Of Foods (AREA)
- Soy Sauces And Products Related Thereto (AREA)
- Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、ショウ油、乳酸飲料、清酒、グルタミン酸ソ
ーダなど多くの食品製造過程で生成するメラノイジン系
色素成分を含むメラノイジン着色液の脱色方法に関する
ものである。更に詳しくは、メラノイジン着色液を、ポ
リアクリロニトリル系の活性炭素繊維（以下「ACF」と
略記することがある）で脱色した後、この使用済みACF
を再生紙、ACFをくり返し脱色用途に使用するメラノイ
ジン着色液の脱色方法に関するものである。TECHNICAL FIELD The present invention relates to a method for decolorizing a melanoidin coloring liquid containing a melanoidin-based pigment component produced in many food manufacturing processes such as show oil, lactic acid beverage, sake, and sodium glutamate. It is a thing. More specifically, the melanoidin coloring liquid is decolorized with a polyacrylonitrile-based activated carbon fiber (hereinafter sometimes abbreviated as “ACF”), and then the used ACF is used.
The present invention relates to a method for decolorizing a melanoidin coloring liquid which is used for repeatedly decolorizing ACF recycled paper and ACF.
（従来技術及び問題点） ショウ油、清酒をはじめ多くの食品の製造過程において
は、アミノカルボニル反応によるメラノイジン系色素成
分が副生し、それによる着色現象が生ずる。(Prior Art and Problems) In the manufacturing process of many foods such as show oil and sake, a melanoidin-based pigment component is by-produced by an aminocarbonyl reaction, and a coloring phenomenon occurs due to it.
従来、ACFを用いたメラノイジン系色素成分の脱色方法
は、特公昭60-17504号公報にて提案され、また、この一
旦使用されたACFの再生方法は、特開昭60-211000号公報
にて提案されている。この再生方法は、ACFを糖液の脱
色に使用した後、５〜20重量％アルカリ水溶液又はアル
コール溶液にて再生する方法である。Conventionally, a method for decolorizing a melanoidin-based pigment component using ACF has been proposed in Japanese Patent Publication No. 60-17504, and a method for regenerating this ACF once used is disclosed in Japanese Patent Laid-Open No. 60-211000. Proposed. This regeneration method is a method in which ACF is used for decolorizing a sugar solution and then regenerated with a 5 to 20 wt% alkaline aqueous solution or an alcohol solution.
この再生方法の場合、再生の初期には80〜95％という高
い性能回復率を示し、かつ劣化する現象は少いが、再生
回数が10〜100回と多くなると、ACFの細孔径及び分布に
変化を生ずるため、脱色能が低下し、性能回復率は60％
以下になるという問題点や繊維強度が低下しやすいとい
う問題点がある。In the case of this regeneration method, a high performance recovery rate of 80 to 95% is shown at the initial stage of regeneration, and the phenomenon of deterioration is small, but when the number of regeneration times increases to 10 to 100 times, the pore diameter and distribution of ACF become large. As the color changes, the decolorizing ability decreases and the performance recovery rate is 60%.
There are the following problems and the problem that the fiber strength tends to decrease.
（発明の目的） 上記のような問題点にかんがみ、再生回数を多くしても
吸着性能の低下や強度の劣化が起りにくい方法が見出さ
れれば、食品工業を中心とした分野での新しいメラノイ
ジン着色液の脱色方法としてきわめて有意義である。(Object of the invention) In view of the above problems, if a method that does not cause deterioration of adsorption performance or deterioration of strength even if the number of times of regeneration is increased is found, new melanoidin coloring in the field centered on the food industry is found. It is extremely meaningful as a decolorizing method for liquids.
本発明は、従来の粉状活性炭や粒状活性炭に比較し、吸
着速度が速く、脱色率が高く、かつ再生使用が可能なAC
Fを吸着材として使用し、しかも再生の際上記したよう
な問題を解決することにある。The present invention, compared to conventional powdery activated carbon or granular activated carbon, has a faster adsorption rate, a higher decolorization rate, and an AC that can be reused.
The purpose is to use F as an adsorbent and solve the above-mentioned problems during regeneration.
（発明の構成） 本発明は、下記の通りである。(Structure of the Invention) The present invention is as follows.
（１）ポリアクリロニトリル系活性炭素繊維を用いてメ
ラノイジン着色液を脱色した後、該活性炭素繊維を0.1
〜4.5重量％のアルカリ液で処理して後酸性水溶液で処
理するか、又は、同アルカリ液と酸性水溶液で処理し、
次いで500〜950℃でガス処理するかして、活性炭素繊維
を再生紙、活性炭素繊維をくり返し使用することを特徴
とするメラノイジン着色液の脱色方法。(1) After decolorizing the melanoidin coloring solution using polyacrylonitrile-based activated carbon fiber,
~ 4.5 wt% alkali solution and then treated with an acidic aqueous solution, or with the same alkaline solution and an acidic aqueous solution,
Then, a method for decolorizing a melanoidin coloring liquid is characterized in that activated carbon fibers are recycled and activated carbon fibers are repeatedly used by gas treatment at 500 to 950 ° C.
（２）酸性水溶液の濃度が、0.1〜3.0重量％である特許
請求の範囲（１）記載のメラノイジン着色液の脱色方
法。(2) The method for decolorizing a melanoidin coloring solution according to claim (1), wherein the concentration of the acidic aqueous solution is 0.1 to 3.0% by weight.
本発明のメラノイジン着色液の脱色方法は、従来の粉状
活性炭や粒状活性炭による脱色方法と比較した場合次の
ような利点がある。The decolorization method of the melanoidin coloring liquid of the present invention has the following advantages when compared with the conventional decolorization method using powdered activated carbon or granular activated carbon.
本発明の場合、１回目の性能回復率が90％以上と高く、
この再生操作を10〜100回とくり返しても回復率を80％
以上保持することが可能である。性能回復率とは下記の
式で示される値をいう。In the case of the present invention, the performance recovery rate of the first time is as high as 90% or more,
Recovery rate is 80% even if this regeneration operation is repeated 10 to 100 times.
It is possible to hold the above. The performance recovery rate is a value represented by the following formula.
A:使用前のACFの脱色率（％） B:再生後のACFの脱色率（％） また、粉状炭、粒状炭に比べ脱色率が高い。 A: Decolorization rate of ACF before use (%) B: Decolorization rate of ACF after regeneration (%) Further, the decolorization rate is higher than that of pulverized coal or granular coal.
本発明の場合、アルカリ濃度が4.5重量％以下と低濃度
であるため、再生回数が増加したも繊維の劣化が少く微
粉末が発生しにくい。In the case of the present invention, since the alkali concentration is as low as 4.5% by weight or less, even if the number of times of regeneration is increased, the fiber is less deteriorated and fine powder is less likely to be generated.
本発明において、吸着材として使用されるACFはポリア
クリロニトリル系（PAN系）ACFである。このPAN系ACFは
既知の方法によって得られるものである。In the present invention, the ACF used as the adsorbent is a polyacrylonitrile (PAN) ACF. This PAN-based ACF is obtained by a known method.
PAN系ACFはフェノール系ACF、セルロース系ACF、ピッチ
系ACFに比べ強度が高く細孔がより拡大しやすく、かつ
メラノイジンに対する親和性が高い。The PAN-based ACF has higher strength than the phenol-based ACF, the cellulose-based ACF, and the pitch-based ACF, the pores are more easily expanded, and the affinity for melanoidin is higher.
そのため脱色率が高い。また、強度が高いゆえに、くり
返し再生しても微粉末の発生が少い。Therefore, the decolorization rate is high. Also, because of its high strength, generation of fine powder is small even after repeated reproduction.
本発明の対象とするメラノイジン着色液の種類は、ショ
ウ油、清酒をはじめどのような種類のものでもよい。す
なわち、メラノイジン着色液は醗酵工程におけるアミノ
カルボニル反応によって生じる、いわゆるメラノイジン
を含む褐色液であり、ショウ油、清酒の外、グルタミン
酸ソーダ溶液、乳酸醗酵溶液等の製造工程において生ず
る着色液である。Type of melanoidins colored liquid to which the present invention is show oil, sake may be of any type including. That is, the melanoidin colored liquid is a brown liquid containing so-called melanoidin generated by an aminocarbonyl reaction in the fermentation process, and is a colored liquid generated in the manufacturing process of soybean oil, sake, sodium glutamate solution, lactic acid fermentation solution and the like.
本発明において使用済みACFの再生に使用するアルカリ
性液の種類としては、特に限定されないが、水酸化ナト
リウムや水酸化カリウム等の水溶液が好ましい。The type of the alkaline liquid used for regenerating the used ACF in the present invention is not particularly limited, but an aqueous solution of sodium hydroxide, potassium hydroxide or the like is preferable.
アルカリ濃度は、0.1〜4.5重量％の範囲であることが必
要である。処理液濃度が4.5重量％を超えると、再生を1
0回、20回更に100回と多数くり返すことにより、ACFの
単繊維強度が低下し、後工程で微粉末が発生しやすくな
る。また、特に好ましい濃度範囲は0.3〜4.0重量％であ
る。アルカリ液による使用済みACFの処理温度は、特に
制限はないが、操作性などからみて20〜95℃が適当であ
る。The alkali concentration needs to be in the range of 0.1 to 4.5% by weight. If the concentration of the treatment liquid exceeds 4.5% by weight, the regeneration will be 1
By repeating a large number of times, such as 0 times, 20 times, and 100 times, the single fiber strength of ACF decreases, and fine powder is likely to be generated in the subsequent process. The particularly preferred concentration range is 0.3 to 4.0% by weight. The treatment temperature of the used ACF with the alkaline solution is not particularly limited, but 20 to 95 ° C is suitable in view of operability and the like.
アルカリ液による処理の後、水洗により残留アルカリを
除去するため、酸性水溶液で処理される。酸性水溶液の
種類としては、塩酸、硝酸、硫酸、燐酸などの水溶液が
ある。処理液の濃度は0.1〜3.0重量％が適当である。処
理液の濃度が3.0重量％を超えると、後工程である水洗
工程での洗浄水の使用量が多量に必要となる。また、処
理液の濃度が0.1重量％未満の場合、アルカリ液で処理
した後のACF中に残存するアルカリが充分に除去されな
いか、又は除去するのに長時間を要することとなる。好
ましい範囲は0.2〜2.0重量％である。処理温度について
は特に制限はないが、前述のアルカリ液による処理と同
様20〜95℃が望ましい。After the treatment with the alkaline solution, it is treated with an acidic aqueous solution in order to remove residual alkali by washing with water. Examples of the acidic aqueous solution include aqueous solutions of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like. The concentration of the treatment liquid is suitably 0.1 to 3.0% by weight. If the concentration of the treatment liquid exceeds 3.0% by weight, a large amount of washing water is required in the subsequent washing step. Further, when the concentration of the treatment liquid is less than 0.1% by weight, the alkali remaining in the ACF after treatment with the alkali liquid is not sufficiently removed or it takes a long time to remove. The preferred range is 0.2-2.0% by weight. The treatment temperature is not particularly limited, but it is preferably 20 to 95 ° C. as in the treatment with the alkaline solution described above.
PAN系ACFを使用した場合、再生が容易であるため0.1〜
4.5重量％のアルカリ液で充分な再生が行われるが、そ
れでも、100回以上になると、性能回復率は80％以下に
低下することがある。この場合は、ガス処理（焼成）に
より再生を行うと、脱色能の回復を有効に達成すること
ができる。When using PAN-based ACF, it is easy to reproduce, so 0.1-
Sufficient regeneration is performed with a 4.5 wt% alkaline solution, but even after 100 times or more, the performance recovery rate may drop to 80% or less. In this case, recovery by degassing can be effectively achieved by regenerating by gas treatment (calcination).
使用済みACFを前記した通りのアルカリ溶液処理後、酸
にて洗浄し、更に水洗し、水洗液のPHが6.0〜8.0になっ
た後、焼成再生を行う。ガス再生処理に使用されるガス
としてはH2O、CO2、N2、NH3、He、Arなどであるが、特
に好ましくはH2O、CO2を含有するガスである。After the used ACF is treated with the alkaline solution as described above, it is washed with an acid and further washed with water, and after the pH of the washing solution reaches 6.0 to 8.0, firing regeneration is performed. The gas used for the gas regeneration treatment is H 2 O, CO 2 , N 2 , NH 3 , He, Ar and the like, but a gas containing H 2 O and CO 2 is particularly preferable.
焼成再生の温度は500〜950℃が好ましく、特に賦活すべ
きACFの製造時の賦活温度を超えないことが、再生時のA
CFの再生収率を高めるために重要なことである。また、
焼成再生温度が、ACF製造時の賦活温度と同等の場合、A
CFの強度低下が生じやすく、かつACFNO吸着特性に変化
が生ずる。The temperature for firing and regeneration is preferably 500 to 950 ° C., in particular, the activation temperature during production of ACF to be activated does not exceed the A during regeneration.
This is important for increasing the CF recovery yield. Also,
If the firing regeneration temperature is equivalent to the activation temperature during ACF production, A
The strength of CF tends to decrease, and the ACFNO adsorption characteristics change.
この焼成再生は、アルカリ液での再生処理の度毎に行う
必要はなく、アルカリ再生処理をくり返し行う過程にお
いて、脱色率が約50〜80％になったとき行えばよい。This firing regeneration does not have to be performed every time the regeneration treatment with the alkaline solution is performed, and may be performed when the decolorization rate becomes about 50 to 80% in the process of repeating the alkali regeneration treatment.
本発明方法の実施態様例をフローシートにて示すと、第
１図の通りである。A flow sheet showing an embodiment of the method of the present invention is as shown in FIG.
第１図は、本発明のメラノイジン着色液の脱色方法の実
施態様例を示すフローシートである。まず、メラノイジ
ン着色液をACFの充填されている吸着塔で処理する。
処理条件としては、SV（空間速度）は５〜1000hr-1、AC
F充填体積に対する処理液の通液倍数はメラノイジン成
分の濃度にもよるが10〜2000倍である。通液中に除去性
能が低下してきた場合、アルカリ水溶液による再生処理
を行う。再生処理に当っては、まず水洗を行う。SVは
５〜1000hr-1、通液倍数は10〜100倍で行われる。FIG. 1 is a flow sheet showing an embodiment of the method for decolorizing a melanoidin coloring liquid of the present invention. First, the melanoidin coloring liquid is treated in an adsorption tower filled with ACF.
As processing conditions, SV (space velocity) is 5 to 1000 hr -1 , AC
The flow rate of the treatment solution to the F filling volume is 10 to 2000 times, depending on the concentration of the melanoidin component. If the removal performance deteriorates during the passage of liquid, a regeneration treatment with an alkaline aqueous solution is performed. In the regeneration treatment, first, washing with water is performed. The SV is performed at 5 to 1000 hr -1 , and the passage rate is 10 to 100 times.
次にアルカリ水溶液にて処理する。SV5〜1000hr-1、
通液倍数10〜1000倍で一方向にアルカリ水溶液を流す
か、又は、アルカリ液をACF充填塔へリサイクルさせ
る。アルカリ水溶液による処理後、水洗を行う。この
水洗の条件はと同じでよい。次に、残っているアルカ
リ分を完全に除去するために酸処理を行う。SV5〜100
0hr-1、通液倍数５〜50倍で行われる。更に、、と
同様の条件で、水洗し、再度原液の脱色に使用す
る。Next, it is treated with an alkaline aqueous solution. SV5 ~ 1000hr -1 ,
Flow the alkali aqueous solution in one direction at a flow rate of 10 to 1000 times or recycle the alkaline solution to the ACF packed column. After the treatment with the alkaline aqueous solution, washing with water is performed. The conditions of this water washing may be the same as. Next, acid treatment is performed to completely remove the remaining alkali content. SV5 ~ 100
It is carried out at 0 hr −1 and a passage rate of 5 to 50 times. Further, under the same conditions as above, the product is washed with water and used again for decolorization of the stock solution.
このように脱色とアルカリ水溶液による再生を３回〜10
0回くり返す。脱色性能が徐々に低下する場合には、ア
ルカリ処理したACFをガス処理により焼成再生する。Thus, decolorization and regeneration with an alkaline aqueous solution are repeated 3 to 10 times.
Repeat 0 times. When the decolorizing performance gradually decreases, the alkali-treated ACF is gas-treated to regenerate it by firing.
（発明の効果） 本発明により下記の効果が得られる。(Effects of the Invention) The following effects are obtained by the present invention.
a.レーヨン系ACF、フェノール系ACFに比べ、アルカリ濃
度が低くてもPAN系ACFの場合は脱着再生が可能であり、
高い性能回復率を示した。Compared to rayon-based ACF and phenol-based ACF, PAN-based ACF enables desorption and regeneration even when the alkali concentration is low.
It showed a high performance recovery rate.
b.低濃度のアルカリ液で再生を行うため、多数のくり返
し再生を行っても、ACFの強度低下が生じにくく、微粉
末の発生が少ない。b. Since regeneration is performed with a low-concentration alkaline solution, even if a large number of repeated regenerations are performed, the ACF strength is less likely to decrease, and the generation of fine powder is small.
c.アルカリ再生と焼成再生を組み合せることにより、更
に高い脱色率を長期間保持することができるようになっ
た。c. By combining alkali regeneration and firing regeneration, it has become possible to maintain a higher decolorization rate for a long period of time.
（実施例と比較例） 実施例中の脱色力試験は、醸造用資材規格協会制定の醸
造用活性炭脱色力試験法に準じACF濃度750ppmにて行っ
たものである。(Examples and Comparative Examples) The decolorizing power test in the examples is carried out at an ACF concentration of 750 ppm in accordance with the bleaching activated carbon decolorizing power test method established by the Brewing Materials Standards Association.
実施例１ 〔ACFの製法〕 アクリロニトリル91.5重量％、メチルメタクリレート8.
0重量％、アクリルアミド0.5重量％よりなる共重合組成
のポリマーを紡糸し、2.0重量％塩酸を用い洗浄を行
い、灰分0.005重量％の54万デニールのアクリル繊維の
トウ（単糸繊度1.5d）を得た。このトウを空気中で240
℃で２時間、更に270℃で0.5時間、自由収縮率の75〜80
％になるような張力で酸化処理したところ、酸素結合量
18.5重量％の酸化繊維を得た。Example 1 [Production method of ACF] Acrylonitrile 91.5% by weight, methyl methacrylate 8.
A polymer having a copolymer composition consisting of 0% by weight and 0.5% by weight of acrylamide was spun, washed with 2.0% by weight of hydrochloric acid, and 540,000 denier acrylic fiber tow with a ash content of 0.005% by weight (single yarn fineness 1.5d) Obtained. 240 this tow in the air
2 hours at ℃, 0.5 hours at 270 ℃, free shrinkage of 75-80
When the oxidation treatment is performed with tension such that
18.5% by weight of oxidized fiber was obtained.
この酸化繊維を賦活温度920℃、炉内圧0.005kg/cm2にて
賦活ガス（H2O／CO2／N2＝5/1/1）により15分間バッチ
的に賦活し、下記の特性を有するACFを得た。This oxidized fiber was activated in batches for 15 minutes with an activation gas (H 2 O / CO 2 / N 2 = 5/1/1) at an activation temperature of 920 ° C and a furnace pressure of 0.005 kg / cm 2 , and the following characteristics were obtained. ACF having was obtained.
比表面積 1,320m2/g 細孔容積 1.10cc/g （トランジショナル孔容積／細孔容積） 0.35 灰分量 0.6重量％ 〔メラノイジン着色液の脱色〕 このACFを用いてトリプトファンメラノイジン溶液の脱
色テストを試みた結果、メラノイジン溶液に対する脱色
率は88％であった。この脱色使用済みのACFを、ACF体積
に対し10倍の温水（80℃）で洗浄し、３重量％の水酸化
ナトリウム水溶液（80℃）にて10分間洗浄した。更にAC
F体積に対し10倍の水で水洗した後、0.3重量％の塩酸水
溶液で５分間浸漬した後、水洗し乾燥した。Specific surface area 1,320m 2 / g Pore volume 1.10cc / g (Transitional pore volume / pore volume) 0.35 Ash content 0.6% by weight [Decolorization of melanoidin coloring liquid] Attempted decolorization test of tryptophan melanoidin solution using this ACF As a result, the decolorization rate for the melanoidin solution was 88%. The decolorized used ACF was washed with 10 times the warm water (80 ° C.) of the ACF volume and washed with a 3 wt% aqueous sodium hydroxide solution (80 ° C.) for 10 minutes. AC
After being washed with 10 times the volume of F water, it was immersed in a 0.3 wt% hydrochloric acid aqueous solution for 5 minutes, then washed with water and dried.
続いて、この乾燥済みのACFを用いて、最初に使用した
のと同じトリプトファンメラノイジン溶液を用いて脱色
テストを行ったところ性能回復率は89％であった。ま
た、上記の脱色、再生を20回くり返した後のACFのトリ
プトファンメラノイジン溶液の脱色性能回復率は80％で
あった。Subsequently, the dried ACF was subjected to a decolorization test using the same tryptophan melanoidin solution as that used initially, and the performance recovery rate was 89%. Further, the recovery rate of the decolorizing performance of the tryptophan melanoidin solution of ACF after repeating the above decolorizing and reproducing 20 times was 80%.
実施例２ 実施例１における第１回再生処理前の使用済みACFを、A
CF体積に対し、10倍の温水（80℃）で洗浄し、更に５倍
の２重量％の水酸化ナトリウム水溶液（80℃）にて10分
間洗浄した。更にACF体積に対し10倍の温水（80℃）で
洗浄した。更に、ACF体積に対し10倍の水で水洗した
後、0.3重量％の塩酸水溶液で５分間浸漬した後、水洗
し、乾燥した。得られたACFのトリプトファンメラノイ
ジンの脱色性能回復率は87％であった。Example 2 The used ACF before the first regeneration treatment in Example 1 was
It was washed with 10 times the warm water (80 ° C.) with respect to the CF volume, and further washed with 5 times the 2 wt% sodium hydroxide aqueous solution (80 ° C.) for 10 minutes. Further, it was washed with warm water (80 ° C.) 10 times the volume of ACF. Further, after washing with water 10 times the volume of ACF, it was immersed in a 0.3 wt% hydrochloric acid aqueous solution for 5 minutes, washed with water and dried. The recovery rate of the decolorizing performance of tryptophan melanoidin of the obtained ACF was 87%.
更に上記の脱色、再生を35回くり返した後、このACFを8
10℃の温度下、スチーム気流中で15分間焼成再生を行っ
た。得られたACFのトリプトファンメラノイジン溶液の
性能回復率は100％であった。また再生収率は97％であ
った。ここで再生収率とは下式で示される。After repeating the above decolorization and reproduction 35 times, this ACF was adjusted to 8
Baking regeneration was performed for 15 minutes in a steam stream at a temperature of 10 ° C. The performance recovery rate of the obtained ACF tryptophan melanoidin solution was 100%. The regeneration yield was 97%. Here, the regeneration yield is represented by the following formula.
C:使用前のACFの重量（ｇ） D:吸着、アルカリ再生及び焼成再生後のACFの重量
（ｇ） 比較例１ 実施例１における第１回再生処理前の使用済みACFを、A
CF体積に対し10倍の温水（80℃）で洗浄し、ACF体積に
対し５倍の15重量％の水酸化ナトリウム水溶液（80℃）
にて10分間洗浄した。更に、ACF体積に対し10倍の水で
水洗した後、0.3重量％の塩酸水溶液で５分間水洗し乾
燥した。 C: weight of ACF before use (g) D: weight of ACF after adsorption, alkali regeneration and calcination regeneration (g) Comparative Example 1 The used ACF before the first regeneration treatment in Example 1 was
Washed with warm water (80 ° C) 10 times the CF volume, and 5% by weight 15% by weight sodium hydroxide aqueous solution (80 ° C) to the ACF volume.
It was washed for 10 minutes. Further, after washing with water 10 times the volume of ACF, it was washed with a 0.3% by weight hydrochloric acid aqueous solution for 5 minutes and dried.
続いて、この乾燥後のACFを用い、最初に用いたものと
同じトリプトファンメラノイジン溶液を用い脱色テスト
を行ったところ、性能回復率は87％であった。更に上記
の脱色、再生を20回くり返した後のACFのトリプトファ
ンメラノイジン溶液の性能回復率は58％であった。操作
においてACFの微粉末が多量発生した。この20回くり返
し再生を行ったACFを、810℃にてスチーム再生に付した
ところ、トリプトファンメラノイジンの脱色性能回復率
は95％と向上したが、微粉末が発生しやすく、再生収率
は64％であった。Subsequently, the ACF after drying was subjected to a decolorization test using the same tryptophan melanoidin solution as that used initially, and the performance recovery rate was 87%. Furthermore, the performance recovery rate of the tryptophan melanoidin solution of ACF after repeating the above decolorization and regeneration 20 times was 58%. A large amount of ACF fine powder was generated during the operation. When this ACF that had been repeatedly regenerated 20 times was subjected to steam regeneration at 810 ° C, the recovery rate of the decolorization performance of tryptophan melanoidin was improved to 95%, but fine powder was easily generated and the regeneration yield was 64%. Met.
第１図は本発明方法の実施態様例を示すフローシートで
ある。FIG. 1 is a flow sheet showing an embodiment of the method of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 康次郎 東京都北区滝野川２―６―30 国税庁醸造 試験所内 審査官 田中 久直 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kojiro Takahashi 2-6-30 Takinogawa, Kita-ku, Tokyo Examiner, Brewing Laboratory, National Tax Agency Hisashio Tanaka
Claims (2)
いてメラノイジン着色液を脱色した後、該活性炭素繊維
を0.1〜4.5重量％のアルカリ液で処理して後酸性水溶液
で処理するか、又は、同アルカリ液と酸性水溶液で処理
し、次いで500〜950℃でガス処理するかして、活性炭素
繊維を再生し、活性炭素繊維をくり返し使用することを
特徴とするメラノイジン着色液の脱色方法。1. A polyacrylonitrile-based activated carbon fiber is used to decolorize a melanoidin coloring solution, and the activated carbon fiber is then treated with an alkali solution of 0.1 to 4.5% by weight and then treated with an acidic aqueous solution. A method for decolorizing a melanoidin coloring solution, which comprises treating with an alkaline solution and an acidic aqueous solution and then gas-treating at 500 to 950 ° C. to regenerate the activated carbon fiber and repeatedly using the activated carbon fiber.
る特許請求の範囲（１）記載のメラノイジン着色液の脱
色方法。2. The method for decolorizing a melanoidin coloring solution according to claim 1, wherein the concentration of the acidic aqueous solution is 0.1 to 3.0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61302780A JPH072213B2 (en) | 1986-12-20 | 1986-12-20 | Decolorization method of melanoidin coloring liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61302780A JPH072213B2 (en) | 1986-12-20 | 1986-12-20 | Decolorization method of melanoidin coloring liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63157968A JPS63157968A (en) | 1988-06-30 |
| JPH072213B2 true JPH072213B2 (en) | 1995-01-18 |
Family
ID=17913027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61302780A Expired - Lifetime JPH072213B2 (en) | 1986-12-20 | 1986-12-20 | Decolorization method of melanoidin coloring liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH072213B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2762087B2 (en) * | 1988-12-26 | 1998-06-04 | 株式会社中埜酢店 | Decolorization method for liquid food |
| JP2740989B2 (en) * | 1991-05-28 | 1998-04-15 | 東邦レーヨン株式会社 | Continuous decolorization and regeneration of food fermented liquid |
| CN102755884A (en) * | 2012-04-13 | 2012-10-31 | 山东轻工业学院 | Method for regenerating waste active carbon by chemical medicament |
-
1986
- 1986-12-20 JP JP61302780A patent/JPH072213B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63157968A (en) | 1988-06-30 |
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