JPS594978B2 - Makubunrihouniyor Netsugi Yokosei Protein - Google Patents

Description

【発明の詳細な説明】 本発明は、熱凝固性蛋白質を含有する水溶液を逆浸透法
又は限外濾過法などの膜分離法で処理する場合、膜分離
洗処理に有効な前処理法として、蛋白質を含有する水溶
液を熱処理して、熱凝固性蛋白質を凝析させ、水溶液中
の膜面汚染物質の負荷を減少させるとともに、凝析した
蛋白質より高品質な蛋白質を回収する膜分離法に有効な
前処理法の改良法に関するものである。DETAILED DESCRIPTION OF THE INVENTION When an aqueous solution containing thermocoagulable proteins is treated by a membrane separation method such as reverse osmosis or ultrafiltration, the present invention provides a pretreatment method that is effective for membrane separation and washing treatment. Effective for membrane separation methods that heat-treat an aqueous solution containing proteins to coagulate thermocoagulable proteins, reduce the load of membrane surface contaminants in the aqueous solution, and recover higher quality proteins than the coagulated proteins. This paper relates to an improved pretreatment method.

熱凝固性蛋白質を含有する水溶液には、馬鈴薯澱粉加工
プロセスにおけるデカンタ−排水、すり身やかまぼこな
どの製造などにおける水産加工排水や、各種食品工業の
製造プロセス溶液など多数ある。There are many types of aqueous solutions containing heat-coagulable proteins, such as decanter wastewater in potato starch processing processes, fishery processing wastewaters in the production of surimi and kamaboko, and manufacturing process solutions in various food industries.

例えば、馬鈴薯澱粉加工の際排出する蛋白質含有のデカ
ンタ−排水は、馬鈴薯澱粉の製造方法により異なるが、
蛋白質４５〜５１％、糖質２５〜３１％、灰分２１〜２
７％、脂肪０．３〜１．０％、全固型分として通常３〜
８％を含有している。For example, the protein-containing decanter wastewater discharged during potato starch processing varies depending on the potato starch manufacturing method.
Protein 45-51%, carbohydrates 25-31%, ash 21-2
7%, fat 0.3-1.0%, total solids usually 3-
Contains 8%.

従って、この排水をそのま５放流すれば、蛋白が腐敗す
るため種々な公害問題を生ずることになる。Therefore, if this wastewater is discharged as it is, the protein will rot and cause various pollution problems.

そこで、この蛋白質を含んだ有価物を回収し排水の処理
も同時にかねる方法が開発されている。Therefore, a method has been developed that allows the recovery of valuable substances containing this protein and the treatment of wastewater at the same time.

この有価物の回収と排水の処理法には、（１）逆浸透法
又は限外濾過法など膜分離法による有価物の回収と水の
再利用法、（２）アベベ方式といわれ、デカンタ−排水
を蛋白質の等電点のｐＨ４，７まで亜硫酸ガスを吹込み
一調整し、９０℃附近まで加熱して蛋白質を凝固沈澱さ
せた後、脱水しフラッシュ乾燥し、蛋白質を回収し、排
水の負荷を軽減する方法、（３）デカンタ−排水を蒸発
法で全量濃縮し、ポテトパルプを吸着剤として飼料とす
る方法などがある。Methods for recovering valuable materials and treating wastewater include (1) a method for recovering valuable materials and reusing water using membrane separation methods such as reverse osmosis or ultrafiltration, and (2) a method known as the Abebe method, which uses a decanter. The wastewater is adjusted to pH 4.7, which is the isoelectric point of the protein, and heated to around 90°C to coagulate and precipitate the protein, then dehydrated and flash-dried to recover the protein and reduce the load on the wastewater. (3) Concentrating the entire amount of decanter wastewater by evaporation and using potato pulp as an adsorbent to feed the feed.

しかし、これらの処理の過程で排水の処理の面からみる
と膜分離法及び全量濃縮法以外は効果は極めて少い。However, in terms of wastewater treatment, these treatments have very little effect except for the membrane separation method and the total concentration method.

一方有価物の回収面からは、これらの凝固蛋白質は、濃
縮されたスラリー状で回収できるが、スラリー濃度が低
く、これを脱水乾燥することが困難で、フィルタープレ
スを用いて脱水するか又は脱水助剤として生石灰を用い
脱水後気流乾燥機で乾燥する方法や、ポテトパルプやフ
スマなど吸着剤を添加して吸着飼料として利用する方法
などが行われているが、添加剤により蛋白質純度が低下
し、利用価値が減少する。On the other hand, from the perspective of recovering valuables, these coagulated proteins can be recovered in the form of a concentrated slurry, but the slurry concentration is low and it is difficult to dehydrate and dry it. Methods include using quicklime as an auxiliary agent and drying in a flash dryer after dehydration, and adding adsorbents such as potato pulp and bran to use as adsorbent feed, but the additives reduce protein purity. , the utility value decreases.

特に蒸発法による全量濃縮の場合は排水に含有する２５
％内外の無機物も全量濃縮されるので、得られる回収有
価物の品質は、不良で利用面で制限されるなど欠点があ
る。In particular, in the case of total concentration using the evaporation method, the amount of 25 contained in wastewater
Since the total amount of inorganic substances within the range of 100% or less is concentrated, there are drawbacks such as the quality of the recovered valuables obtained is poor and its use is limited.

また、水産加工排水の場合は、魚肉蛋白質や魚油が混在
しているので、通常の加圧浮上法、電解浮上法、凝集沈
澱法などにより懸濁物処理を主体とした２次処理をして
魚肉蛋白質や魚肉を回収することが行われている。In addition, in the case of fishery processing wastewater, since it contains fish protein and fish oil, secondary treatment mainly consisting of suspended solids treatment is carried out using the usual pressure flotation method, electrolytic flotation method, coagulation sedimentation method, etc. Fish protein and fish meat are being recovered.

しかし、これらの２次処理では１０００〜２０００ ｐ
ｐｍ以下の水溶性蛋白質や油脂分の除去は困難であるの
で、そのま５排水としては放流できないので、さらに活
性スラッジ法や逆浸透法などの膜分離法などによる３次
処理を行う必要がある。However, in these secondary treatments, 1000 to 2000 p
Since it is difficult to remove water-soluble proteins and fats and oils below pm, it cannot be discharged as wastewater as it is, so it is necessary to perform tertiary treatment using membrane separation methods such as activated sludge method and reverse osmosis method. .

また、２次処理で得られた回収有価物は勿論、従来の一
般的な膜分離法による有価物の回収処理では濃縮スラリ
ー液を乾燥粉化する際、蛋白質とともに油脂分もかなり
混在するため良品質な回収有価物を得ることができない
などの欠点があった。In addition, in addition to the recovered valuables obtained in the secondary treatment, when the concentrated slurry liquid is dried and powdered in the conventional general membrane separation method, a considerable amount of oil and fat is mixed together with the protein, so it is not a good idea. There were drawbacks such as the inability to obtain high-quality recovered valuables.

本発明者らは、熱凝固性蛋白質含有水溶液から、灰分の
少い高品位蛋白質を効率よく回収し、有価物として付加
価値の高い有効利用法を検討するとともに、高次排水処
理を目的とする排水処理プロセスについて種々研究を行
ってきた結果本発明に到達した。The present inventors efficiently recover high-grade protein with low ash content from an aqueous solution containing heat-coagulable protein, and investigate effective ways to use it as a valuable resource with high added value, with the aim of high-level wastewater treatment. As a result of conducting various studies on wastewater treatment processes, we have arrived at the present invention.

即ち、本発明は熱凝固性蛋白質含有水溶液中に加熱蒸気
又は加熱空気を直接吹込み、蛋白質を凝固させ、引続き
真空冷却器で瞬間的に減圧脱気処理し、力いる水溶液中
の水分の蒸発、脱臭並びに液温の冷却を行うとともに、
凝析した蛋白質を機械的に分離し、良質な高蛋白質含有
有価物を副次的に回収するとともに、膜分離性処理に有
効な水溶液を得ることを特徴とする膜分離性処理のため
の蛋白質含有水溶液の前処理改良法である。That is, the present invention directly blows heated steam or heated air into a thermocoagulable protein-containing aqueous solution to coagulate the protein, and then instantaneously depressurizes it in a vacuum cooler to evaporate water in the aqueous solution. In addition to deodorizing and cooling the liquid temperature,
Protein for membrane-separable treatment, characterized by mechanically separating coagulated proteins, secondary recovery of high-quality, high-protein-containing valuables, and obtaining an aqueous solution effective for membrane-separable treatment. This is an improved pre-treatment method for containing aqueous solutions.

本発明の方法によると加圧容器又はインライン中で熱凝
固性蛋白質含有水溶液中に、ｐＨ調整など前処理をする
ことなく、又必要があれば凝析した蛋白質の再溶解を防
止するため、ｐＨを等電点前後に調整した後、加圧蒸気
を直接吹込み８０〜１２０℃、好ましくは９５〜１００
℃で２〜３０分間好ましくは５〜１０分間加熱し、熱凝
固性蛋白質を４０〜６０％凝固析出させ、膜分離処理に
おける負荷を減少させるとともに場合によっては、存在
する活性酵素類を失活させ、同時に微生物の汚染など後
処理工程での品質変化を防ぎ、その後直ちに処理液を真
空冷却器に導き断熱膨腸により、瞬間的に水分を蒸発さ
せ、真空度に応じ液を冷却させ、蒸気による水溶液の加
熱により生じた増成量を脱気により少くとも等量もしく
は８０％程度を除去し、後処理での処理水量負荷を減少
させ、同時に脱法による適正処理上限温度５０〜５５℃
まで低下させる。According to the method of the present invention, a thermocoagulable protein-containing aqueous solution is heated in a pressurized container or in-line without any pretreatment such as pH adjustment, and if necessary, the pH is adjusted to prevent redissolution of the coagulated protein. After adjusting the isoelectric point to around the isoelectric point, pressurized steam is directly blown into the temperature at 80-120°C, preferably 95-100°C.
℃ for 2 to 30 minutes, preferably 5 to 10 minutes, to coagulate and precipitate 40 to 60% of thermocoagulable proteins, reduce the load on membrane separation treatment, and in some cases, deactivate active enzymes present. At the same time, it prevents quality changes in the post-processing process such as microbial contamination, and immediately after that, the treated liquid is introduced into a vacuum cooler and the water is instantly evaporated by an adiabatic expander, and the liquid is cooled according to the degree of vacuum. At least the same amount or about 80% of the increased amount generated by heating the aqueous solution is removed by degassing, reducing the load on the amount of water to be treated in post-treatment, and at the same time, the upper limit temperature for proper processing by degassing is 50 to 55°C.
lower to

又加熱法として場合によっては加熱空気を使用すること
によって液量の増加を防ぐことができる。Further, an increase in the amount of liquid can be prevented by using heated air as the heating method depending on the case.

その後、このスラリーは遠心分離操作により固液分離を
行うか、又は直接そのま５、膜分離処理へと導かれる。Thereafter, this slurry is subjected to solid-liquid separation by centrifugation, or directly 5 to a membrane separation process.

この真空冷却処理により、水溶液中の凝固蛋白質のスラ
リーの固液分離が容易になるとともに蛋白質との結合塩
や含有油脂分の蛋白質からの分離を良好ならしめ、さら
に遠心脱水による固液分離の良好さはケーキ水分の減少
となり灰分や油脂分合量の少い高品位蛋白質を極めて経
済的に得ることが可能となった。This vacuum cooling treatment facilitates the solid-liquid separation of the coagulated protein slurry in the aqueous solution, and also improves the separation of binding salts and fats and oils from the protein, and further improves the solid-liquid separation by centrifugal dehydration. As a result, the moisture content of the cake is reduced, making it possible to obtain high-quality protein with low ash and fat content extremely economically.

また遠心分離による懸濁物質の除去には、通常デカンタ
−や超遠心分離器など機械的方法が用いられるが、本発
明の場合、バスケット型連続遠心分離機例えば米国シャ
ープレス社のフレツチャーなどが好適である。Further, mechanical methods such as a decanter or an ultracentrifuge are normally used to remove suspended solids by centrifugation, but in the case of the present invention, a basket-type continuous centrifuge such as Fletcher manufactured by Sharpless, Inc. in the United States is suitable. It is.

なおまた場合によっては上述の遠心脱水処理をしないで
凝析蛋白質含有スラリーはそのまま直ちに逆浸透膜又は
限外濾過膜装置へ供給され脱法による適当な脱塩濃縮又
は脱糖分、脱塩による蛋白質分離などの選択的分離濃縮
処理をうけ、濃縮処理液はドラム乾燥、スプレー乾燥な
どの乾燥粉末化処理を行い、透過処理水はそのまま放流
するか、再利用水として使用するか又はその他水質に応
じた適切な処理を行う。In addition, in some cases, the slurry containing coagulated proteins is directly supplied to a reverse osmosis membrane or ultrafiltration membrane device without performing the above-mentioned centrifugal dehydration treatment, and is subjected to appropriate desalination concentration or sugar removal by desalination, protein separation by desalination, etc. After undergoing selective separation and concentration treatment, the concentrated treated liquid is subjected to drying and powdering treatment such as drum drying or spray drying, and the permeated water is either discharged as is, used as recycled water, or treated in other appropriate ways depending on the water quality. Perform processing.

本発明の実施例を示すと次の通りである。Examples of the present invention are as follows.

実施例 １ 馬鈴薯澱粉加工プロセスから発生した蛋白質４８％、糖
質２７％、灰分２４％、脂肪０．５％からなる固型分５
％を含有する１ｍ／ｈｒのデカンタ−排水に、インライ
ンに設けられたスチームインジェクターより、３ｋｇ／
ｃｒｉｔの加圧蒸気を排水中に直接吹込み加熱加圧した
後、凝固蛋白質含有スラリーを０．５ ｍ３の真空冷却
器に導き脱気し５０℃まで冷却させる。Example 1 Solid content 5 consisting of 48% protein, 27% carbohydrates, 24% ash, and 0.5% fat generated from the potato starch processing process
3 kg/hr from a steam injector installed in-line to the 1 m/hr decanter waste water containing %
After pressurized steam of crit is directly blown into the waste water and heated and pressurized, the coagulated protein-containing slurry is introduced into a 0.5 m3 vacuum cooler, degassed, and cooled to 50°C.

その後巴工業−米国シャープレス社製バスケット型遠心
脱水機フレツシャーで１１５ Ｏｒｐｍ、９００Ｇで遠
心脱水しケーキを得るとともに、蛋白分離液はそのまま
膜分離装置に導き、膜面積１０ｄ、操作圧力５０ｋｇ／
ｆｆｌ流速１．４ ｍ ／ｓｅｃでダイセル株式会社製
ＤＲ８−９０の膜を用い逆浸透性処理し、可溶蛋白質、
糖質、灰分からなる有価物の回収を行い、透過処理水ば
ＢＯＤ４０００ｐｐｍの無色透明水を得フリーム用水と
して再使用した。Thereafter, a cake was obtained by centrifugal dehydration at 115 Orpm and 900G using a basket-type centrifugal dehydrator Flesher manufactured by Tomoe Kogyo - US Sharpless Company, and the protein separation liquid was directly introduced into a membrane separation device with a membrane area of 10 d and an operating pressure of 50 kg/cm.
Reverse osmosis treatment was performed using a DR8-90 membrane manufactured by Daicel Corporation at a flow rate of 1.4 m/sec to remove soluble proteins,
Valuable substances consisting of carbohydrates and ash were recovered, and colorless transparent water with a BOD of 4000 ppm was obtained from the permeation treatment and reused as freem water.

またさらに高品位蛋白質を得る場合は限外沢過法で操作
圧力３ ｋｇ／ａｔ’ｔ、流速２７ｎ、／ｓｅｃでダイ
セル株式会社製ＤＵＹ−２０の膜を用い限外沢過し、蛋
白質６２％、糖質２９％の高品位蛋白質含有有価物を得
ることができた。In order to obtain even higher quality protein, ultrafiltration was performed using a DUY-20 membrane manufactured by Daicel Corporation at an operating pressure of 3 kg/at't and a flow rate of 27 n/sec using the ultrafiltration method to obtain 62% protein. We were able to obtain a high-grade protein-containing valuable product containing 29% carbohydrates.

いま、前処理における各種加熱条件と得られた回収有価
物の性状並びに脱法処理における膜汚染指数（膜分離装
置において運転開始１．時間後の透水速度をφ１．，１
２時間運転後の透水速度をφφｔ２とした時、透水速度
の経時低下の度合を示す膜汚染指数は−ｍ＝ｌｏｇφｔ
ｌ−１ｏｇφｔ２／ｌｏｇ△ｔ（△ｔ＝ｌ ｔ２− ｔ
、 Ｉ ） で示される。Now, we will discuss various heating conditions in the pretreatment, the properties of the recovered valuables, and the membrane contamination index in the demethod treatment (the water permeation rate 1 hour after the start of operation in the membrane separator is φ1., 1
When the water permeation rate after 2 hours of operation is φφt2, the membrane contamination index indicating the degree of decrease in water permeation rate over time is -m=logφt
l-1ogφt2/log△t(△t=l t2-t
, I).

こ５では、ｔ ｒ＝ １ ｈｒ、 ｔ２＝ ３００ ｈ
ｒとして膜汚染指数を算出した）との関係を示すと次表
の通りであった。In this 5, t r = 1 hr, t2 = 300 h
The relationship between the membrane contamination index (the membrane contamination index was calculated as r) is shown in the following table.

この結果からスチームインジェクションによる蛋白凝固
に際し品質面、脱法処理の点から９５〜１００℃まで加
熱することが最も好ましいことが判る。From this result, it can be seen that it is most preferable to heat the protein to 95 to 100° C. from the viewpoint of quality and process removal during protein coagulation by steam injection.

実施例 ２ スケソウダラの加工排水並びにすり身製造における晒水
の混合排水〔固型分３％（蛋白質７７％、油脂分７％、
糖質３％、灰分１３％）〕を６０メツシュのバイブレー
ティングスクリーンにより粗濾過した後、実施例１と同
一装置を用いインラインでスチームインジェクターより
５ ｋｇ ／ｃｒｉ’ｔの加熱蒸気を排水中に直接吹込
み加熱加圧しん後、凝固蛋白質含有スラリーを真空冷却
器に導き、脱気し５０℃まで冷却させた。Example 2 Mixed wastewater from pollack processing and bleaching water from surimi production [solid content 3% (protein 77%, oil and fat content 7%,
3% carbohydrate, 13% ash] was coarsely filtered through a 60-mesh vibrating screen, and then 5 kg/cri't of heated steam was directly injected into the wastewater from an in-line steam injector using the same equipment as in Example 1. After blowing, heating, and pressurizing, the coagulated protein-containing slurry was introduced into a vacuum cooler, degassed, and cooled to 50°C.

その後実施例１と同一の遠心脱水機を用い同一条件でス
ラリーの脱水を行い、その分離液はそのまま膜分離装置
に導き実施例１と同一な逆浸透性処理を行った。Thereafter, the slurry was dehydrated using the same centrifugal dehydrator as in Example 1 under the same conditions, and the separated liquid was directly introduced into the membrane separation device and subjected to the same reverse osmosis treatment as in Example 1.

いま、前処理における各種加熱条件と得られた回収物の
性状並びに脱法処理における膜汚染指数との関係を示す
と次表の通りである。The following table shows the relationship between the various heating conditions in the pretreatment, the properties of the recovered material, and the membrane contamination index in the removal treatment.

この結果からスチームインジェクションによる蛋白凝固
真空冷却法は結合塩及び油脂分の少い良質な高純度の蛋
白質を得るとともに、逆浸透洗処理に好適な前処理法と
なることが判る。These results show that the protein coagulation vacuum cooling method using steam injection not only yields high-quality, high-purity protein with a low content of binding salts and fats and oils, but also serves as a suitable pretreatment method for reverse osmosis washing.

Claims (1)

【特許請求の範囲】[Claims] １ 熱凝固性蛋白質含有水溶液の膜分離洗処理に際し、
該水溶液中に加熱蒸気又は加熱空気を直接吹込み、蛋白
質を凝固させ、引続き真空冷却器で、瞬間的に減圧脱気
処理し、該水溶液中の水分の蒸発、脱臭並びに液温の冷
却を行うとともに、凝析した蛋白質を機械的に分離し、
良質な高蛋白質含有有価物を副次的に回収するとともに
、膜分離洗処理に有効な水溶液を得ることを特徴とする
前処理改良法。1 During membrane separation and washing treatment of aqueous solutions containing thermocoagulable proteins,
Heated steam or heated air is directly blown into the aqueous solution to solidify the protein, followed by instantaneous vacuum degassing treatment in a vacuum cooler to evaporate water in the aqueous solution, deodorize it, and cool the liquid temperature. At the same time, the coagulated proteins are mechanically separated,
An improved pretreatment method characterized by secondary recovery of high-quality, high-protein-containing valuables and obtaining an aqueous solution effective for membrane separation and washing treatment.