JPS58111945A - Rinsing method for film or photographic paper - Google Patents
Rinsing method for film or photographic paperInfo
- Publication number
- JPS58111945A JPS58111945A JP20936581A JP20936581A JPS58111945A JP S58111945 A JPS58111945 A JP S58111945A JP 20936581 A JP20936581 A JP 20936581A JP 20936581 A JP20936581 A JP 20936581A JP S58111945 A JPS58111945 A JP S58111945A
- Authority
- JP
- Japan
- Prior art keywords
- water
- washing
- activated carbon
- silver
- fixing
- 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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
- G03D3/00—Liquid processing apparatus involving immersion; Washing apparatus involving immersion
- G03D3/02—Details of liquid circulation
- G03D3/06—Liquid supply; Liquid circulation outside tanks
- G03D3/065—Liquid supply; Liquid circulation outside tanks replenishment or recovery apparatus
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photographic Processing Devices Using Wet Methods (AREA)
- Photographic Developing Apparatuses (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、カラー写真漂白定着処理後の水洗水（以下水
洗廃水と記す）から効率的に水を水洗水としてリサイク
ルする方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for efficiently recycling water from washing water (hereinafter referred to as washing wastewater) after color photographic bleach-fixing processing as washing water.
一般写真処理においてフィルムや印画紙は、処理薬品が
残在するとその保存性に著しい障害をもたらすために非
常に多くの水洗水を用いて薬品を洗い流している。フィ
ルム及び印画紙中に含有する処理薬品は水洗処理槽に移
動する際、これら！真材料に付着して水洗処理槽内に持
ら込まれ水洗廃水として廃棄されていた。定着処理薬品
は、銀を始めとして少量多種類の無機及びｈ機薬品から
成る。これらの薬品の中には、生物学的Ｓ＊＊求最（Ｂ
ＯＤ）や化学的酸素要求−（ＣＯＤ）の高い物質が含ま
れるため、水洗廃水をそのまま廃棄すると環境汚染の原
因となる。また、水洗廃水中の銀は低濃度であるが、廃
水の壷が多いため銀の総饅は少なくなく高価な銀を回収
することは、非常に大きな意義がある。従って、水洗廃
水から銀と水を効率的に回収し、しかも水は水洗水とし
てリサイクルすることは非常に大きな経済的価値がある
。しかし従来、水洗廃水から銀と水を同時にしかも経済
的に回収するｈ￥には確立されておらず未回収のまま廃
棄されていた。In general photographic processing, a large amount of washing water is used to wash away the chemicals from film and photographic paper, since the presence of residual processing chemicals significantly impairs their storage stability. When processing chemicals contained in film and photographic paper are transferred to the washing tank, these! It adhered to the actual materials and was carried into the washing treatment tank, where it was disposed of as washing wastewater. Fixing chemicals consist of small amounts of various inorganic and organic chemicals, including silver. Some of these drugs contain biological S**
Because it contains substances with high chemical oxygen demand (OD) and chemical oxygen demand (COD), disposing of washing wastewater as it is causes environmental pollution. In addition, although the concentration of silver in washing wastewater is low, since there are many jars of wastewater, the total amount of silver is small, and recovering expensive silver is of great significance. Therefore, it is of great economic value to efficiently recover silver and water from washing wastewater and to recycle the water as washing water. However, until now, it has not been established that silver and water can be recovered simultaneously and economically from washing wastewater, and the silver and water have been disposed of unrecovered.
写真漂白定着水洗水から銀のみを回収する方法としては
、特公昭５５−１５２１３７号として、銀を電気分解法
にて分離回収する方法が提案されている。また別の方法
としては、特公昭５５−１６１０３４号があり、銀を重
金属吸着用キレート樹脂に吸着分離する方法もある。As a method for recovering only silver from photographic bleach-fixing washing water, a method has been proposed in Japanese Patent Publication No. 55-152137 in which silver is separated and recovered by electrolysis. Another method is disclosed in Japanese Patent Publication No. 55-161034, in which silver is adsorbed and separated on a chelate resin for adsorbing heavy metals.
いずれの方法においても銀の１収はともかく処理後廃水
を水洗水としてリサイクルできないこと、廃水員が多く
銀の濃度が低いため回収装置が大型になり、しかも回収
操作が煩雑である等の欠点があった。勿論、従来の方法
を用いて水と銀を夫々回収することもできたが、これら
の場合には回収プロセスが複雑となるための設備費、処
理費用とも＾くなり中小規模のカラー現像所やラボでは
到底工業的に実施することはできなかった。In either method, although the silver yield is 1, the wastewater after treatment cannot be recycled as washing water, and the recovery equipment is large due to the large number of wastewater workers and the low silver concentration, and the recovery operation is complicated. there were. Of course, it was possible to recover water and silver separately using conventional methods, but in these cases, the recovery process would be complicated and the equipment and processing costs would be high, making it difficult for small and medium-sized color photo labs and It could not be carried out industrially in a laboratory.
本発明は写真の定着処理における水洗廃水め濃縮並びに
水の回収を同時にしかも工業的規模で実施し得る方法を
提供するものである。The present invention provides a method that allows concentration of washing waste water and recovery of water in photographic fixing processing to be carried out simultaneously on an industrial scale.
即ち、本発明は、写真の定着処理後の洗滌廃水を逆浸透
法により、溶存物質を濃縮回収することにより、該廃水
から実質的に銀などの有価値成分を回収し、該逆浸透プ
ロセスから排出した水は次いで活性炭と接触させること
により、前記写真の定着処理後の洗滌水などとしてリサ
イクル使用するにある。That is, the present invention uses reverse osmosis to concentrate and recover dissolved substances from washing wastewater after photographic fixing processing, thereby substantially recovering valuable components such as silver from the wastewater, and removing waste from the reverse osmosis process. The discharged water is then brought into contact with activated carbon and recycled for use as washing water after fixing the photograph.
本発明で用いる逆浸透処理は、従来公知の逆浸透膜を用
いる脱塩、又は薬剤の濃縮方法及び装置が制限なく用い
られる。例えば酢酸セルローズ、芳香族ポリアミド、ポ
リビニルアルコール、ポリサル７オン等で作られた躾を
用いた逆浸透モジュールは東洋紡績株式会社、東−株式
会社、Ｄｕ Ｐｏｎｔ社等称、また逆浸透処理装置に
ついては笹愈機械株式会社、栗田工業株式会社、エバラ
インフィルコ株式会社などが夫々製造販売している。For the reverse osmosis treatment used in the present invention, conventional desalting using a reverse osmosis membrane or drug concentration methods and devices can be used without limitation. For example, reverse osmosis modules that use a material made of cellulose acetate, aromatic polyamide, polyvinyl alcohol, polysal 7one, etc. are manufactured by Toyobo Co., Ltd., Toyo Co., Ltd., Du Pont Co., Ltd., etc., and reverse osmosis treatment equipment is manufactured by companies such as Toyobo Co., Ltd. They are manufactured and sold by Sasayu Kikai Co., Ltd., Kurita Kogyo Co., Ltd., Evaline Philco Co., Ltd., and others.
また活性炭処理については、粉体混合形、粒状活性炭に
よる吸着塔形及びその他の公知の接触方法が制限なく使
用し得る。使用される活性炭も特に制限なく使用される
。これらは、例えばクラレケミカル株式会社、武田薬品
工業株式会社、カルコン社などが製造販売している。Regarding the activated carbon treatment, a powder mixture type, an adsorption tower type using granular activated carbon, and other known contact methods can be used without limitation. The activated carbon used is also used without any particular restriction. These are manufactured and sold by, for example, Kuraray Chemical Co., Ltd., Takeda Pharmaceutical Co., Ltd., and Calcon Co., Ltd.
逆浸透装置は、その指定最大圧力で運転されるが、多く
の場合、イれは５０ｋｇ／ｃｍ〜５５ｋｇ／ｃｊ’（７
）闇にある。写真の定着処理後の洗浄廃水と処理する場
合には、この許容最大圧力の範囲内で極力＾辻にするの
が、分離性能、処理能力の点から好ましい。Reverse osmosis equipment is operated at its specified maximum pressure, but in many cases the leakage is between 50 kg/cm and 55 kg/cj' (7
) in the darkness. When treating the cleaning wastewater after photographic fixing, it is preferable to keep the pressure within this allowable maximum pressure range as much as possible from the viewpoint of separation performance and processing capacity.
本発明の主要な利点は、逆浸透膜によって水洗廃水中の
銀を含む無機及び有機薬品をほぼ完全に分離濃縮し、膜
透過水中にごくわずか透過する有機薬品について活性炭
処理すれば水洗水として再びリサイクルすることができ
ることを見出し、その結果、水洗水の大幅な節水ができ
たことにある。他方、濃縮された水洗廃水は、その量が
少働でしかも銀などの有価値成分の濃度も高く、従来公
知の回収方法、例えば銀であれば硫化銀として容易に沈
澱回収することができる。The main advantage of the present invention is that inorganic and organic chemicals including silver in washing wastewater can be almost completely separated and concentrated using a reverse osmosis membrane, and organic chemicals that pass through the membrane-permeated water in a very small amount can be treated with activated carbon and recycled as washing water. We discovered that it can be recycled, and as a result, we were able to save a lot of water for washing. On the other hand, the concentrated washing wastewater has a small amount of water and has a high concentration of valuable components such as silver, and can be easily recovered by conventional recovery methods, for example, silver can be precipitated and recovered as silver sulfide.
あるいは、濃縮水洗水を定着処理行程へフィードバック
することも可能であるが、この場合は、フィードバック
する濃縮水洗水の組成、濃度は、定着処理構内の液と同
じになるように新らたに薬品を添加して調整しなければ
ならない。Alternatively, it is possible to feed back the concentrated washing water to the fixing process, but in this case, new chemicals are added so that the composition and concentration of the fed-back concentrated washing water are the same as the solution in the fixing process. must be adjusted by adding.
以下本発明を添付図面によって説明する。The present invention will be explained below with reference to the accompanying drawings.
第１図社、本発明の一実施態様を示す写真材料処理装置
の側面図であり、１は定着処理水槽、２Ａ、２Ｂ、２Ｃ
は各々水洗水槽、３は逆浸透処理工程、４は活性炭処理
工程をそれぞれ示す。処理されるべき写真材料は、上記
各処理槽１．２Ａ１２Ｂ、２Ｃを順次移送されて処理が
行われる。水洗水槽２Ｃには５より水道水などの洗滌水
が供給される。水洗用水槽は第１図に示すごとく多段の
カスケード方式で給水が行われるのが一般的である。Fig. 1 is a side view of a photographic material processing apparatus showing one embodiment of the present invention, in which 1 is a fixing water tank, 2A, 2B, 2C
3 indicates a water washing tank, 3 indicates a reverse osmosis treatment process, and 4 indicates an activated carbon treatment process. The photographic material to be processed is sequentially transferred to each of the processing tanks 1.2A12B and 2C and processed therein. Washing water such as tap water is supplied from 5 to the washing water tank 2C. Water is generally supplied to a water tank for washing in a multi-stage cascade system as shown in FIG.
水洗水槽２Ａからオーバーフローした水洗廃水は、逆浸
透処理Ｉ８３で分離濃縮され、６より排出し、膜透過水
は活性炭処理工程４で水中に残存する有機物質等を除去
した後、水洗水槽２０へリサイクルされる。この場合、
水洗水槽２０へ供給する新しい水の腸は、逆浸透処理に
５−
より排出される濃縮水洗廃水膳とほぼ等しい量でよい。The washing wastewater that overflows from the washing water tank 2A is separated and concentrated by reverse osmosis treatment I83 and discharged from 6, and the membrane permeated water is recycled to the washing water tank 20 after removing organic substances remaining in the water in the activated carbon treatment step 4. be done. in this case,
The amount of fresh water supplied to the washing tank 20 may be approximately equal to the amount of concentrated washing waste water discharged from the reverse osmosis treatment.
本発明において、リサイクルする水の水質は、水洗水槽
２Ｇへ供給される水と同程度かそれ以上の水質であるこ
とが必要である。リサイクルする水の水質が悪いと、運
転を行っているうちに水洗水機内へ不純物が徐々に蓄積
７し、フィルムや印画紙に悪影響を及ぼす。リサイ
クルする水の量は、水洗廃水の濃度、組成及び逆浸透工
程で使用する逆浸透膜の分離性能、あるいは回収メリッ
トの経済性等を総合的に評価して、適宜決定すればよい
。本発明のリサイクルホロは、特に規定されるものでは
ないが、逆浸透モノシール供給湯の５０〜９０％回収す
るのがよい。In the present invention, it is necessary that the quality of the water to be recycled be equal to or higher than that of the water supplied to the washing tank 2G. If the quality of the recycled water is poor, impurities will gradually accumulate in the washer during operation, which will have a negative impact on film and photographic paper. The amount of water to be recycled may be determined as appropriate by comprehensively evaluating the concentration and composition of the washing wastewater, the separation performance of the reverse osmosis membrane used in the reverse osmosis process, the economical benefits of recovery, and the like. Although the recycled holo of the present invention is not particularly specified, it is preferable that 50 to 90% of the reverse osmosis MonoSeal supplied hot water be recovered.
回収率が例えば５０％以下の如く低いと経済的に不利で
あり、また９０％以上になると、一般に透過水の水質が
悪くなり、活性炭処理４における負荷が増大し好ましい
。If the recovery rate is low, such as 50% or less, it is economically disadvantageous, and if it is 90% or more, the quality of the permeated water generally deteriorates and the load on the activated carbon treatment 4 increases, which is preferable.
活性炭処理における吸着方法はバッチ式、カラム式いず
れでもよいが、カラム式は膜透過水を直接カラムへ通水
することが可能であるため連続的に処理水が得られると
ともに、供給系ンプを取り付ける必要がないたや好適で
ある。カラム式の場合は、通水速度ＳＶＩ〜２０で行う
ことが可能であるが、好ましくはＳＶ５〜１０が効率よ
く６−
有機物質を吸着できる。The adsorption method for activated carbon treatment can be either batch or column type, but column type allows membrane permeate water to be passed directly to the column, so treated water can be obtained continuously, and a supply system pump can be attached. Although it is not necessary, it is preferable. In the case of a column type, it is possible to conduct the water flow at a water flow rate of SVI to 20, but preferably a water flow rate of SV5 to 10 can efficiently adsorb organic substances.
一方、逆浸透処理における濃縮廃水は、銀等の回収ある
いは、再利用の工程に使用される。On the other hand, concentrated wastewater from reverse osmosis treatment is used in the recovery or reuse process of silver and the like.
以下、本発明を実施例をあげて説明するが本発明はこれ
に限定されるものではない。The present invention will be described below with reference to Examples, but the present invention is not limited thereto.
実施例１
第１図に示す工程を用い、逆浸透膜として東洋紡輪株式
会社の＾圧用酢酸セルロース躾を組み込んだ徳山曹達株
式会社製逆浸透装ＭＲＯ−Ｈ−２型（モージュール１本
）で水洗水を逆浸透処理した。Example 1 Using the process shown in Fig. 1, a reverse osmosis system MRO-H-2 model (1 module) manufactured by Tokuyama Soda Co., Ltd., which incorporated Toyobo Co., Ltd.'s ^-pressure cellulose acetate membrane as a reverse osmosis membrane, was used. The washing water was subjected to reverse osmosis treatment.
試料水溶液として銀２Ｍ（１，化学的酸素要求量１５０
／Ｑを含有するカラー写真漂白定着処理後の水洗水を上
記逆浸透膜へ圧力５５ｋｇ／ａｉｄ通水速度４１７分で
供給した。Silver 2M (1, chemical oxygen demand 150
Washing water after the color photographic bleach-fixing process containing /Q was supplied to the reverse osmosis membrane at a pressure of 55 kg/aid and a water flow rate of 417 minutes.
この時の膜透過水量は、３．２６／分で回収率８０％に
調整した。この水を内径２００龍φ、高さ５００ｓｉｇ
のヤシガラ粒状活性炭を充填したカラムへ通水したが、
処理後の水質は、銀２ｗ、ｏ／Ｑ、化学的酸素要求量５
−ａ／（ｌであった。At this time, the amount of water permeated through the membrane was adjusted to 3.26/min to give a recovery rate of 80%. This water has an inner diameter of 200mm and a height of 500sig.
Water was passed through a column packed with coconut shell granular activated carbon.
Water quality after treatment: silver 2w, o/Q, chemical oxygen demand 5
-a/(l).
この活性炭処理水を水洗水槽ヘリサイクルする操作を１
ケ月間連続して行ったが、この間印画紙の変色等の経時
変化はまったくみられなかった。Step 1 is to recycle this activated carbon treated water to the washing tank.
The test was carried out continuously for several months, and no changes over time such as discoloration of the photographic paper were observed during this period.
第１図は、本発明のブ０セスのフローシートである。
１は処理水槽、２Ａ１２Ｂ及び２Ｃは夫々水浄槽、３は
逆浸透処理工程、４は活性炭処理工程を夫々示す。
特許出願人
徳山曹達株式会社FIG. 1 is a flow sheet of the process of the present invention. 1 is a treated water tank, 2A12B and 2C are water purification tanks, 3 is a reverse osmosis treatment process, and 4 is an activated carbon treatment process. Patent applicant: Tokuyama Soda Co., Ltd.
Claims (1)
を逆浸透処理し、得られた透過水を活性炭処理した後、
該フィルム又は印画紙の洗浄水として再使用することを
特徴とするフィルム又は印画紙の水洗方法。 ２、逆浸透処理により濃縮された回収液を定着処理工程
にリサイクルする特許請求の範曲第１項記載の方法。[Scope of Claims] 1. After undergoing reverse osmosis treatment of the washing waste liquid of the film or photographic paper that has undergone the fixing treatment process and treating the obtained permeated water with activated carbon,
A method for washing film or photographic paper, characterized in that the water is reused as washing water for the film or photographic paper. 2. The method according to claim 1, wherein the recovered liquid concentrated by reverse osmosis treatment is recycled to the fixing treatment step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20936581A JPS58111945A (en) | 1981-12-25 | 1981-12-25 | Rinsing method for film or photographic paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20936581A JPS58111945A (en) | 1981-12-25 | 1981-12-25 | Rinsing method for film or photographic paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58111945A true JPS58111945A (en) | 1983-07-04 |
| JPH0145908B2 JPH0145908B2 (en) | 1989-10-05 |
Family
ID=16571726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20936581A Granted JPS58111945A (en) | 1981-12-25 | 1981-12-25 | Rinsing method for film or photographic paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58111945A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991016667A1 (en) * | 1990-04-19 | 1991-10-31 | Devappa Dr. Ing. R. Zinsser & Ing. K. Prestl | Developing device for photographic coating substrates |
| JPH05210228A (en) * | 1992-01-31 | 1993-08-20 | Fuji Photo Film Co Ltd | Photograph forming device |
| EP0609769A2 (en) * | 1993-02-05 | 1994-08-10 | Du Pont De Nemours (Deutschland) Gmbh | Method and apparatus for recycling wash water in photographic processing |
-
1981
- 1981-12-25 JP JP20936581A patent/JPS58111945A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991016667A1 (en) * | 1990-04-19 | 1991-10-31 | Devappa Dr. Ing. R. Zinsser & Ing. K. Prestl | Developing device for photographic coating substrates |
| JPH05210228A (en) * | 1992-01-31 | 1993-08-20 | Fuji Photo Film Co Ltd | Photograph forming device |
| EP0609769A2 (en) * | 1993-02-05 | 1994-08-10 | Du Pont De Nemours (Deutschland) Gmbh | Method and apparatus for recycling wash water in photographic processing |
| DE4303379A1 (en) * | 1993-02-05 | 1994-08-11 | Du Pont Deutschland | Process and apparatus for washing water recycling in photographic processing |
| EP0609769A3 (en) * | 1993-02-05 | 1997-04-16 | Du Pont Deutschland | Method and apparatus for recycling wash water in photographic processing. |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0145908B2 (en) | 1989-10-05 |
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