Processing method or photographic processing waste liquor

A disposal device for photographic processing waste liquor which concentrates the photographic process waste liquor by evaporation. The disposal device has a gas detecting device for detecting gas which may be generated during the evaporation of the waste liquor and a control device for stopping the evaporation based on the detection of a concentration of a specific gas. The processing method for photographic waste liquor involves evaporating the waste liquor to concentrate it and detecting gases which are generated during the evaporation process. When the concentration of a specific gas reaches a certain level, the evaporation step is halted.

BACKGROUND OF THE INVENTION 
This invention relates to a disposal device for evaporation disposal of 
waste liquor generated as by developing processing of a photographic 
light-sensitive material, by The invention refers to a device for use with 
automatic developing machine for photography (hereinafter abbreviated to 
as "photographic processing waste liquor" or "waste liquor"), particularly 
to a disposal device for photographic processing waste liquor suitable for 
disposal as arranged with an automatic developing machine or in the 
vicinity of an automatic developing machine. 
Generally speaking, photographic processing of a light-sensitive silver 
halide photographic material has been performed by combining the steps by 
use of processing liquors having one or more of the functions such as 
developing, fixing, water washing, etc. in the case of black-and-white 
light-sensitive materials, and color developing, bleach-fixing (or 
bleaching and fixing), water washing, stabilizing, etc. in the case of 
color light-sensitive material. 
In photographic processing in which a large amount of light-sensitive 
materials are processed, the components consumed by processing are 
supplemented, while the components thickened dissolution or evaporation in 
the processing liquor by processing (e.g. bromide ion in a developing 
solution, or silver complexes in a fixing solution) are removed to 
maintain the components in the processing liquor at constant levels. 
According to such means, supplementing solutions are supplemented into the 
processing liquors, and a part of the processing liquors are discharged 
for removal of the thickened components in the photographic processing. 
In recent years, there is a trend in which the amount supplemented of 
solutions including washing water which is supplementing liquid for water 
washing is reduced to great extent for the reasons in pollution or 
economy, but photographic processing waste liquor is led through a waste 
liquor pipe from the processing tank of the automatic developing machine, 
and diluted with waste water of washing water or cooling water of the 
automatic developing machine before being discarded into sewage, etc. 
However, due to strengthened pollution regulation in recent years, although 
discarding of washing water or cooling water into sewage or rivers may be 
possible, discarding of photographic processing liquors other than these 
[e.g. developing solution, fixing solution, color developing solution, 
bleach-fixing solution (or bleaching solution and fixing solution), 
stabilizing solution, etc.] is substantially practically impossible. For 
these reasons, the respective photographic processing dealers are using to 
professional waste liquor disposal dealers for recovery of waste liquor 
with recovery fee or have pollution disposal equipments installed. 
However, using waste liquor dealers requires considerable space for 
storage of waste liquor, and it is very expensive in cost. Further, the 
pollution disposal equipment is extremely large in initial cost, and also 
considerable vast place is required for installation to disadvantage. 
Accordingly, waste liquor is generally recovered by waste liquor recovery 
dealers to be detoxified by secondary and tertiary disposal. However, the 
waste liquor receipt price is not only becoming higher year by year due to 
increased recovery fee, but also due to poor recovery efficiency in 
mini-laboratories, etc., recovery order can be responded to with 
difficulty, whereby there ensues such problem that waste liquors are 
filled in the store, etc. 
For solving these problems, for the purpose of effecting disposal of 
photographic processing waste liquor easily in mini-laboratories, etc., 
studies have been made to evaporate water and then dry or solidify 
suspended component of the photographic processing waste liquor by 
heating, as disclosed in Japanese Provisional Utility Model Publication 
No. 70841/1985. 
Whereas, in the case of evaporation concentration of photographic 
processing waste liquor, the properties of the precipitates will change 
with progress of evaporation concentration whereby the precipitates will 
lose fluidity to be discharged from the processing section with 
difficulty. Accordingly, one may consider to set the processing time for 
evaporation concentration by metering photographic processing waste 
liquor, etc., but the working to meter the amount and set the processing 
time depending on the respective processing volume is cumbersome. 
Accordingly, means for detecting the change in properties of the 
precipitates by evaporation concentration easily have been variously 
studied, and consequently it has been found that specific sulfur type 
compounds frequently used in fixing solution or bleach-fixing solution 
contained in photographic processing waste liquor by evaporation 
concentration, for example, thiosulfates or sulfites are decomposed to 
change the properties of the precipitates, whereby fluidity is lost, and 
also sulfurous acid gas, hydrogen sulfide gas are generated. Accordingly, 
by detecting the gas concentration generated by evaporation concentration, 
thereby stopping evaporation concentration, there can be obtained 
precipitates which can be easily taken out. 
SUMMARY OF THE INVENTION 
The present invention has been accomplished in view of the problems of the 
prior art as described above, and is intended to provide a disposal device 
for photographic processing waste liquor which stops the disposal from the 
gas concentration generated by evaporation concentration of photographic 
processing waste liquor to obtain precipitates which can be easily taken 
out. 
The present invention, in order to solve the above problems, provides a 
disposal device for photographic processing waste liquor by heating 
photographic processing waste liquor to effect evaporation concentration, 
comprising a gas detecting means for the gas concentration generated in 
disposal of said photographic processing waste liquor and a control means 
for stopping concentration disposal on the basis of the gas concentration 
from the gas detecting means equipped therein. 
Also, the present invention provides a processing method of photographic 
processing waste liquor having evaporation concentration processing, which 
comprises the steps of detecting gases generated in the evaporation 
concentration processing of the photographic processing waste liquor; and 
then stopping said evaporation concentration processing on the basis of a 
concentration of a specific gas among the detected gases.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 
When photographic processing waste liquor is heated by a heating means to 
be evaporated and concentrated, the concentration of the specific gas is 
detected by a gas detecting means and disposal of evaporation 
concentration is stopped at a predetermined level of gas concentration by 
a control means. Accordingly, the changes in the properties of the 
precipitates with progress of evaporation concentration of photographic 
processing waste liquor can be prevented and this control is performed by 
detection, and therefore control of stopping evaporation concentration of 
the gas concentration can be simply done. 
The gas detecting means may be those which can detect gases generated as 
well as detect the concentration of a separated specific gas or those 
which can detect only the concentration of a specific gas, but preferably 
be a sensor for detecting hydrogen sulfide gas and/or sulfurous acid gas. 
As the sensor detecting such gases, there are, for example, semiconductor 
sensor, constant potential electrolytic system sensor, disphragm Gaval 
system, etc. In this invention, for example, there may be employed the 
sensors as described in "Practical Handbook of Chemical Sensor", published 
by Kabushiki Kaisha Fuji Technosystem; "Technical Development of New 
Sensor and Optimum Selection and Use", published by Keiei Kaihatsu Center, 
Publishing Division; and "Collection of Sensor Application Technologies", 
published by Kabushiki Kaisha Keiei System Kenkyusho, etc. 
Also, in the present invention, for stopping evaporation concentration, it 
is preferred to deodorize the odor by spraying a deodorant. The position 
where the gas concentration is detected is not limited to the inside of 
the evaporation batch where evaporation concentration is effected, but it 
can be also located at the place where cooling, condensing means or liquid 
reservoir tank is located, further inside or outside of the main device in 
which these disposal sections are housed. 
The detected gas concentration for stopping evaporation concentration 
disposal, for one kind of gas, should be preferably set in the range from 
0.1 to 1000 ppm, more preferably from 1 to 100 ppm, particularly 
preferably from 2 to 20 ppm. 
Further, as the deodorizer, deodorant for deodorizing the odor, there may 
be employed the deodorizers, deodorants as described in "Development and 
Application of New Deodorizers", published by Kabushiki Kaisha Toray 
Research Center, and deodorizers, deodorants, in the specifications of the 
Patents as described on pp. 143 to 161 thereof. 
When a gas is detected, deodorizing can be effected by adding a compound in 
the concentrate in the evaporating means. Examples of such compound may 
include hydroxides of metals such as KOH, NaOH, Ca(OH).sub.2, NH.sub.4 OH, 
Mg(OH).sub.2, LiOH and other hydroxides of Al, Ba, Be, Ce, Co, Cu, Fe, Zn, 
etc. As salts of the above metals, there may be included carbonates, 
bicarbonates, phosphates, borates, sulfites, further other alkaline buffer 
agents, organic acid salts, alkali metal salts of chelating agents, etc. 
Preferably, KOH, NaOH, Ca(OH).sub.2, NH.sub.4 OH, Fe(OH).sub.3, 
carbonates, sulfites, preferably the compounds as mentioned above may be 
formed into an aqueous solution, which is delivered into the evaporation 
means by actuating a pump based on the gas detecting signal. The amount 
may be preferably in the range from 0.1 to 500 g, particularly from 1 to 
50 g per one liter of the concentrate. Further, it may be also preferred 
to use K.sub.2 CO.sub.3 and K.sub.2 SO.sub.3 in combination. 
Further, as the control when hydrogen sulfide gas is detected, if the gas 
concentration exceeds the set value, the heating means is stopped, the 
deodorant is liberated and supplementing of photographic processing waste 
liquor is stopped. After a certain period of time, cooling fan, air 
circulation pump, etc. are also stopped. In this case, when the deodorant 
is liberated into the evaporation means, in order to maintain the 
deodorizing effect, the heating means is stopped after elapse of a certain 
period of time, for example, 10 minutes, followed by stopping of driving 
of other devices similarly, etc. However, these operations are not 
limitative of the present invention. 
The heating means in contact with photographic processing waste liquor in 
the present invention may be a nichrome wire, or a heater molded by 
working such as cartridge heater, quartz heater, Teflon (trade name) 
heater, rod heater or panel heater, or heating by microwave may be 
possible. Also, an electroconductive material may be directly contacted 
with photographic processing waste liquor, and current may be passed 
through the electroconductive material into photographic processing waste 
liquor, thereby effecting heating. 
The electroconductive material may be constituted by selecting at least one 
composition from among single crystalline Si, polycrystalline Si, Ta.sub.2 
N, Ta-SiO.sub.2, ZrO.sub.2, ZrN, TiN, Cr-Si-O, SiC, SiC-Zr, SiC-Cr, 
SiC-Hf, SiC-Ti, SiC-Mo, SiC-W, SiC-Nb, SiC-Ta, SiC-La, B, B-Mo, B-La, 
B-Cr, B-Tr, B-Na, B-Ta, W, B-W, B-V, C, C-halogen, C-Si, C-Ge, C-H, Pt, 
Mo, Mo-Si, MoSi.sub.2, CaO, MgO, Y.sub.2 O.sub.3, La.sub.2 (CrO.sub.4), 
and can suppress generation of odor generated during evaporation 
concentration by catalytic action, influence from current, etc. Also, the 
above composition may be preferably used merely as the resistance material 
to be formed into a heater insulated against photographic processing waste 
liquor, and further ceramic heater, etc. may be available. 
The heating means is arranged so that the whole may be dipped into 
photographic processing waste liquor, or alternatively arranged so that a 
part may be dipped therein, and evaporation of such photographic 
processing waste liquor may be preferably effected by heating by means of 
a heating means for accomplishing improvement of waste liquor disposal 
efficiency (disposal speed), and the heating temperature may be preferably 
about 120.degree. to 130.degree. C. 
The evaporation means may assume any desired form, including cubic body, 
cylindrical column, polygonal column, typically square column, cone, 
polygonal pyramid, typically tetragonal pyramid, or a combination of some 
of them, but it is preferably shaped longitudinally lengthy so that the 
temperature difference of photographic processing waste liquor between the 
vicinity of the heating means and the bottom may be greater. Further, in 
order to reduce blow-out accident by abrupt boiling as far as possible, 
the space above the waste liquor surface in the evaporation means should 
be preferably made as broad as possible. 
The material for the evaporation means may be any material if it is 
heat-resistant, such as heat-resistant glass, titanium, stainless steel, 
carbon steel, heat-resistant plastic, etc., but from the standpoint of 
safety and corrosion resistance, stainless steel (preferably SUS 304 or 
SUS 316, particularly preferably SUS 316) or titanium may be preferred. 
The evaporation means is equipped with a heating means for heating 
photographic processing waste liquor preferably to about 120.degree. to 
130.degree. C., and this may be also located in the waste liquor but it is 
also possible to heat the waste liquor in the evaporation means through 
the wall of the evaporation means by providing it externally of the 
evaporation means. The heating means may be located at any position where 
waste liquor in the evaporation means can be heated, but it is preferred 
to locate the heating means so as to heat the upper portion of the 
photographic processing waste liquor in the evaporation means, thereby 
creating difference in temperature between the photographic processing 
waste liquor in the vicinity of the heating means and the bottom of the 
photographic processing waste liquor, as described in Japanese Provisional 
Patent Publication No. 141692/1988, and it is preferred for enhancing the 
effect of the present invention to locate the heating means so that the 
temperature difference may become 5.degree. C. or higher. 
This invention has a condensing means which cools and condenses the vapor 
evaporated, and for condensing means can be adopted all kinds of heat 
exchange means, which may be any constitution of (1) the shell and tube 
type (polytubular type, muffled tube type), (2) the double tubular type, 
(3) the coil type, (4) the spiral type, (5) the plate type, (6) the fin 
tube type, (7) the trombone type and (8) the air-cooling type. 
Also, the heat exchange type reboiler technique can be used and (1) the 
vertical thermosiphon type, (2) the horizontal thermosiphon type, (3) the 
overflow tubular type (kettle type), (4) the compulsory circulation type, 
(5) the internal insertion type, etc. may be employed. 
Further, the heat exchange technique of the condenser system may be 
employed, namely either one of (1) the direct condenser system, (2) the 
tower built-in system, (3) the tower top location system, (4) the 
separation system, etc. 
It is also possible to use a cooler, and any desired system of cooler may 
be available. The air-cooled system heat exchanger can be also 
advantageously used, which may be either of (1) the forced aeration system 
and (2) the blown aeration system. 
According to a preferred embodiment, the condensing means is constituted of 
a heat dissipating device having a heat dissipating plate (fan for air 
cooling) located at the vapor discharging pipe for discharging evaporated 
vapor, and has a means for feeding water on the heat dissipating plate. In 
this case, water may be preferably fed in shower from above the heat 
dissipating device onto the heat dissipating plate. Water may be also fed 
onto the heat dissipating plate through a valve or an electromagnet valve, 
if necessary, from, for example, a plug of tap water. In this case, the 
means for feeding water refers to a plug of tap water, a water feeding 
pipe, etc., but preferably stored water may be fed onto the heat 
dissipating plate through various quantitative or non-quantitative 
metering pumps as described above. Particularly preferably, it is 
constituted that stored water may be circulated in such a manner that 
water in the water tank provided below the heat dissipating plate device 
is fed in shower through a pump onto the heat dissipating plate and again 
stored in the water tank below. In this case, a liquid level sensor is 
preferably provided in the stored water tank and a signal emitted when the 
liquid level becomes lower than a certain level, whereby exhaustion of 
stored water can be known and water can be fed again. 
The condensing means is constituted of a heat dissipating plate device 
having a heat dissipating plate (fan for air cooling) located at the vapor 
discharging pipe for discharging evaporated vapor, and when it possesses a 
means for feeding water on the heat dissipating plate, it preferably have 
a motor fan for air cooling at the same time. Particularly, in this case, 
the motor fan for air cooling should be provided so that the air may be 
passed through the heat dissipating plate device to be discharged out of 
the evaporation concentration disposal device of the present invention, 
because condensation at the electrically armored portion within the 
evaporation concentration disposal device of the present invention can be 
prevented. 
The condensate obtained by cooling and condensing the evaporated vapor is 
stored in a tank for storing condensate (stored liquid tank), and the 
stored liquid tank is preferably located internally of the evaporation 
concentration device of the present invention for making the space 
smaller, and in this case, the stored liquid tank is preferably located on 
a stand capable of being withdrawn for making workability better. 
Further, the constitutions of the evaporation means, heating means and 
condensing means of the present invention are described in detail in 
Japanese Patent Applications No. 69435/1987, No. 69436/1987 and No. 
69437/1987 previously filed by the present applicant. 
Next, as to typical examples of photographic processing waste liquor for 
which disposal according to the present invention can be applied, those as 
described in Japanese Patent Application No. 194615/1987 can be used. 
Particularly, in the evaporation concentration disposal device of the 
present invention, photographic processing waste liquor containing large 
amounts of thiosulfates, sulfites, ammonium salts and organic acid ferric 
complex salts can be effectively disposed, and extremely effective when 
containing organic acid ferric complexes and thiosulfates. 
BRIEF DESCRIPTION OF THE DRAWINGS 
FIG. 1 is a diagrammatic representation of an automatic developing machine. 
FIG. 2 is a diagrammatic representation of a disposal device for 
photographic processing liquor of the present invention. 
As a preferred application example of the present invention, the present 
device is suitable for performing disposal of photographic processing 
waste liquor generated with developing processing of a light-sensitive 
photographic material by an automatic developing machine within the 
automatic developing machine or in the vicinity thereof. Here, the 
automatic developing machine and photographic processing waste liquor are 
explained. 
Automatic developing machine 
In FIG. 1, the automatic developing machine is shown by the reference 
numeral 100, and one shown in the figure is of the system in which a 
roll-shaped light-sensitive photographic material F is guided continuously 
through a color developing tank CD, a bleach-fixing tank BF and a 
stabilizing processing tank Sb to perform photographic processing and 
after drying D, wound up. The reference numeral 101 is a supplementing 
solution tank, and the photographic processing amount of the 
light-sensitive photographic material F is detected by a sensor 102, and 
following the detected information, the supplementing solution is 
supplemented to each processing tank by the control device 103. 
When the supplementing solution is supplemented to each photographic 
processing tank, overflowed waste liquor is discharged from the processing 
tank and collected in the stock tank 104. As the means for transferring 
the overflowed photographic processing waste liquor to the stock tank 104, 
a simple method is to permit the waste liquor to fall naturally through a 
guide pipe. It can be sometimes also compulsorily transferred by means of 
a pump, etc. 
Also, as described above, although there is difference in components in the 
photographic processing tanks, CD, BF, Sb, in the present invention, it is 
preferred to mix all the photographic processing liquors and dispose the 
mixture comprehensively. 
EXAMPLES 
FIG. 2 illustrates schematically a constitution of the disposal device for 
photographic processing liquor of the present invention. 
In the figure, the reference numeral 1 is an evaporation kettle as the 
evaporation means, which is constituted of a cylindrical columnar upper 
part 1a with larger diameter and a cylindrical columnar lower part 1b with 
smaller diameter, the lower part 1b being provided with a heating means 2, 
and further below with a ball valve 3. The evaporation kettle 1 is 
provided with a liquid level sensor 4, and further on a supporting stand 5 
arranged at the lower part 1b of the evaporation kettle 1 is mounted a 
sludge receiver 6, and the sludge receiver 6 is provided below the lower 
part 1b, and a bag 7 made of polypropylene is fixed by an O-ring 8 
internally thereof. At the upper part 1a of the evaporation kettle 1 is 
provided with a vapor discharging pipe 9, and the vapor discharging pipe 9 
is connected through a heat exchanger 10 and a condensing means 11 to a 
stored liquid introducing pipe 12. 
In the condensing means 11, a number of heat dissipating plates 13 for 
cooling are provided at the vapor discharging pipe 9, and further a liquid 
level sensor 14 is provided. At the lower part of the condensing means 11 
is provided a cooling water introducing pipe 15, which is connected 
through a cooling water circulating pump 16 to a shower pipe 17 perforated 
with a number of small holes. 
The air within the condensing means 11 is discharged by a motor fan 18 for 
air cooling out of the disposal device. The stored liquid introducing pipe 
12 is connected into the stored liquid tank 19, and the tip end 12a of the 
stored liquid introducing pipe 12 is positioned below the stored liquid 
surface in the stored liquid tank 19 to constitute a bubbling mechanism 
20. Further, at the upper part of the stored liquid tank 19 is provided an 
activated charcoal cartridge 21 for housing activated charcoal. The stored 
liquid tank 19 is provided with an air introducing pipe 22, and its tip 
end 22a is introduced through an air pump 23 into the waste liquor in the 
evaporation kettle 1. Reference numeral 24 is a waste liquor feeding tank, 
which is provided with a waste liquor introducing pipe 25 and connected 
through a Bellows pump 26 and a heat exchanger 10 to the upper part 1a of 
the evaporation kettle. The waste liquor feeding tank 24 is further 
provided with a liquid level meter 27. 
The upper part 1a of the evaporation kettle 1 is further provided with a 
guide pipe 28, which is connected through a plunger disc 29 to the waste 
liquor feeding tank 24, and the upper part 1a of the evaporation kettle 1 
is also provided with a temperature sensor 30. 
The upper part 1a of the evaporation kettle 1 is equipped with a gas sensor 
60 and a deodorant sprayer 61; the supplementing portion of photographic 
processing waste liquor with a gas sensor 62 and a deodorant sprayer 63; 
the condensing means 11 with a gas sensor 64 and a deodorant sprayer 65; 
the main device internally with a gas sensor 66, a deodorant 67; and 
further the main device externally with a gas sensor 68, a deodorant 
sprayer 69. The detection signals from these gas sensors 60, 62, 64, 66 
and 68 are inputted into the control means 70, and when the gas 
concentrations are higher than the values set respectively at the gas 
sensors at the control means 70, it derives the deodorant driving means 71 
to actuate the deodorant sprayers 61, 63, 65, 67 and 69, and further 
drives the running stopping means 72 to stop actuation of the 
predetermined disposal device. 
Next, the outline of the process of heating, evaporation disposal by use of 
this device is to be explained. 
About 20 liters of the overflowed liquid from the automatic developing 
machine are stored in the waste liquor feeding tank 24, and to the stored 
liquid tank 19 are connected the activated charcoal cartridge 21 filled 
with activated charcoal, the stored liquid introducing pipe 12 and the air 
introducing pipe 22. Within the sludge receiver 6 below the lower part 1b 
of the evaporation kettle 1, the bag 7 made of polypropylene was placed 
and fixed with two O-rings 8 to the lower part 1b of the evaporation 
kettle 1. After water is fed into the condensing means 11, the switch is 
turned on, whereby the air pump 23 is actuated and the air within the 
stored liquid tank 19 is introduced through the air introducing pipe 22 
into the evaporation kettle 1 and the air is released from the tip end 22a 
located further below the heating means 2. 
Then, the motor fan 18 for air cooling and the cooling water circulation 
pump 16 are actuated in this order, the stored water passing through the 
cooling water introducing pipe 15 is fed to the shower pipe 17 or onto the 
heat dissipating plate 13 of the vapor discharging pipe 9 housed within 
the condensing means 11 and again stored at the lower part of the 
condensing means 11. Circulation occurs in such a manner. 
Through actuation of Bellows pump 26, the waste liquor within the waste 
liquor feeding tank 24 passes through the waste liquor introducing pipe 
25, then through the heat exchange means 10 and is delivered into the 
evaporation kettle 1. When the waste liquor amount in the evaporation 
kettle 1 is increased and the liquid level is detected by the liquid level 
sensor 4 for, for example, 3 seconds or longer actuation of the Bellows 
pump 28 stops, simultaneously with the switch being turned on at the 
heating means 2 to initiate heating evaporation. 
Evaporation concentration is effected by heating evaporation, and the air 
is introduced through the feeding pipe 70 and by such stirring, the vapor 
bubbles are released at early stage and the bubbles are fine. Accordingly, 
heating decomposition can be alleviated to lower the odor gas existing in 
the vapor generated by evaporation concentration to great extent, whereby 
generation of hydrogen sulfide, sulfur type odor can be alleviated even 
when concentration may be proceed. Owing to this effect, when the liquid 
amount of the waste liquor in the evaporation kettle 1 is reduced to lower 
the liquid level, and the liquid level becomes to be not detected by the 
liquid level sensor 4 for 3 seconds or longer, the switch of the Bellows 
pump 26 is again turned on to repeat the actuation that the waste liquor 
in the waste liquor feeding tank 24 is fed into the evaporation tank 1. 
The vapor evaporated from the evaporation tank 1 passes through the vapor 
discharging pipe 9, and the vapor is subjected to heat exchange with waste 
liquor in the heat exchanger 10, and then passes through the condensing 
means 11, whereby a part of the vapor is condensed to become condensate. 
The condensate passes together with the residual gas in the vapor through 
the stored liquid introducing pipe 12, is delivered into the stored liquid 
tank 19, released through the tip end 12a below the stored liquid surface, 
and the condensate is stored within the stored liquid tank 19. At this 
time, bubbling is effected by ascending of the gas released from below the 
stored liquid surface through the stored liquid, and by the effect of 
bubbling, the gas such as hydrogen sulfide, etc. dissolved in the stored 
liquid is expelled out of the liquid, and the gas is returned by actuation 
of the air pump 23 through the air introducing pipe 22 from the stored 
liquid tank 19 to the photographic processing waste liquor positioned at 
the lower part within the evaporation kettle 1. 
The stored liquid tank 19 is communicated to the air through the activated 
charcoal cartridge 21 filled with activated charcoal, whereby release of 
odor into the air is prevented. 
When exhaustion of the waste liquor within the waste liquor feeding tank 24 
is detected by the liquid level sensor 27, actuating of the Bellows pump 
26 stops, the switch of the heating means 2 is turned off, the cooling 
water circulation pump 16, the motor fan 18 for air cooling will stop two 
hours later, simultaneously with lighting of a lamp and buzzing of a 
buzzer to inform completion of the evaporation concentration disposal, and 
also the air pump 23 stops. Here, by opening the ball valve 3, the sludge 
in the evaporation kettle 1 is permitted to fall into the bag 7 made of 
polypropylene, and then the bag taken out by detaching O-ring 8. 
In the process of evaporation concentration, when exhaustion of the stored 
water in the condensing means 11 is detected by the liquid level sensor 
14, the lamp is lighted, simultaneously with buzzing of a buzzer to inform 
exhaustion of the stored water. 
In the process of evaporation concentration, when the liquid level in the 
evaporation kettle 1 is lowered for some reason and the temperature sensor 
30 detects elevation of the temperature in the evaporation kettle 1 to 
120.degree. C. by heating in absence of liquid, the lamp is lighted 
simultaneously with buzzing of an alarm buzzer, and also the switch of the 
heating means 2 is turned off, and thereafter the evaporation 
concentration disposal is intermitted according to a series of actuations 
as described above. 
Further, as shown by the broken line in FIG. 2, deodorants 73 and 74 can be 
also provided internally or externally of the main device, and the 
location places are not limited, but they can be arranged at any desired 
place. 
EXPERIMENTAL EXAMPLE 1 
By use of an automatic developing machine RP-800 for MPS processing system 
paper (produced by Konica Corporation), a commercially available paper for 
color photography (produced by Konica Corporation) was subjected to 
picture printing, followed by continuous processing by use of the 
following processing steps and processing liquors. 
______________________________________ 
Standard processing steps: 
______________________________________ 
(1) Color developing 40.degree. C. 
3 min. 
(2) Bleach-fixing 38.degree. C. 
1 min. 30 sec. 
(3) Stabilizing 25.degree. C.-35.degree. C. 
3 min. 
(4) Drying 75.degree. C.-100.degree. C. 
about 2 min. 
______________________________________ 
Processing liquor compositions: 
______________________________________ 
(Color developing tank solution) 
Ethylene glycol 15 ml 
Potassium sulfite 2.0 g 
Potassium bromide 1.3 g 
Sodium chloride 0.2 g 
Potassium carbonate 24.0 g 
3-Methyl-4-amino-N-ethyl-N-(B-methane- 
5.5 g 
sulfonamidoethyl)aniline sulfate 
Fluorescent brightener (4,4'-diamino- 
1.0 g 
stilbenedisulfonic acid derivative) 
Hydroxylamine sulfate 3.0 g 
1-Hydroxyethylidene-1,1-diphosphonic acid 
0.4 g 
Hydroxyethyliminodiacetic acid 
5.0 g 
Magnesium chloride hexahydrate 
0.7 g 
Disodium 1,2-dihydroxybenzene-3,5-disulfonate 
0.2 g 
Made up to one liter with addition of water and 
adjusted to pH 10.20 with potassium hydroxide and 
sulfuric acid. 
(Color developing supplementing solution) 
Ethylene glycol 20 ml 
Potassium sulfite 3.0 g 
Potassium carbonate 24.0 g 
Hydroxylamine sulfate 4.0 g 
3-Methyl-4-amino-N-ethyl-N-(B-methane- 
7.5 g 
sulfonamidoethyl)aniline sulfate 
Fluorescent brightener (4,4'-diamino- 
2.5 g 
stilbenedisulfonic acid derivative) 
1-Hydroxyethylidene-1,1-diphosphonic acid 
0.5 g 
Hydroxyethyliminodiacetic acid 
5.0 g 
Magnesium chloride hexahydrate 
0.8 g 
Disodium 1,2-dihydroxybenzene-3,5-disulfonate 
0.3 g 
Made up to one liter with addition of water and 
adjusted to pH 10.70 with potassium hydroxide and 
sulfuric acid. 
(Bleach-fixing tank solution) 
Ferric ammonium ethylenediaminetetraacetate 
60.0 g 
dihydrate 
Ethylenediaminetetraacetic acid 
3.0 g 
Ammonium thiosulfate (70% solution) 
100.0 ml 
Ammonium sulfite (40% solution) 
27.5 ml 
Made up to the total amount of one liter with addition 
of water and adjusted to pH 7.1 with potassium 
carbonate or glacial acetic acid. 
(Bleach-fixing supplementing solution A) 
Ferric ammonium ethylenediaminetetraacetate 
260.0 g 
dihydrate 
Potassium carbonate 42.0 g 
Made up to the total amount of one liter with addition 
of water and adjusted to pH 6.7 .+-. 0.1 with acetic 
acid or aqueous ammonia. 
(Bleach-fixing supplementing solution B) 
Ammonium thiosulfate (70% solution) 
250.0 ml 
Ammonium sulfite (40% solution) 
25.0 ml 
Ethylenediaminetetraacetic acid 
17.0 g 
Glacial acetic acid 85.0 ml 
Made up to the total amount of one liter with addition 
of water and adjusted to pH 5.3 .+-. 0.1 with acetic 
acid or aqueous ammonia. 
(stabilizing solution and supplementing 
solution substituting for water washing) 
Ethylene glycol 1.0 g 
2-Methyl-4-isothiazolin-3-one 
0.20 g 
1-Hydroxyethylidene-1,1-diphosphonic acid 
1.0 g 
(60% aqueous solution) 
Ammonia water (25% aqueous ammonium 
2.0 g 
hydroxide solution) 
Made up to one liter with water and adjusted to pH 7.0 
with 50% sulfuric acid. 
______________________________________ 
The automatic developing machine was filled with the above color developing 
tank solution, bleach-fixing tank solution and stabilizing tank solution, 
and the running test was conducted while treating the above commercially 
available color photographic paper sample and supplementing the above 
color developing supplementing solution, bleach-fixing supplementing 
solutions A and B, and the stabilizing supplementing solution through the 
Bellows pump. The amounts supplemented per 1 m.sup.2 of the color paper 
were respectively 190 ml as the supplemented amount to the color 
developing tank, each 50 ml of the bleach-fixing supplementing solutions A 
and B to the bleach-fixing tank and 250 ml of the stabilizing 
supplementing solution substituting for water washing to the stabilizing 
tank. The stabilizing tanks in the automatic developing machine were made 
the first to the third tank in the direction of flow, and a multi-tank 
countercurrent system was employed in which supplementing was effected 
from the final tank, the overflowed solution from the final tank was 
permitted to flow into the tank in the preceding stage, and further the 
overflowed solution therefrom into the tank in the preceding stage. 
Continuous processing was performed until the total amount of the 
stabilizing solution substituting for water washing supplemented became 
3-fold of the stabilizing tank volume. 
After color negative films GX-100 (produced by Konica Corporation) were 
exposed in the conventional manner, by use of an automatic developing 
machine obtained by modification of a negative film processor NPS-FP34 
(produced by Konica Corporation), continuous processing was performed 
under the developing processing conditions shown below. 
______________________________________ 
Amount 
Time Tempera- Tank supple- 
Processing hr., ture volume mented 
step min. .degree.C. 
liter ml/dm.sup.2 
______________________________________ 
Color developing 
3'15" 38 .+-. 0.3 
18 15 
Bleach-fixing 
2'00" 38 .+-. 0.3 
15 -- 
first tank 
Bleach-fixing 
2'00" 38 .+-. 0.3 
15 10 
second tank 
No washing stabi- 
1'00" 38 .+-. 0.3 
9 -- 
lizing first tank 
No washing stabi- 
1'00" 38 .+-. 0.3 
9 10 
lizing second tank 
Stabilizing 40" 38 .+-. 0.3 
9 10 
Drying 1'30" 38 .+-. 0.3 
______________________________________ 
From the no water washing stabilizing (second tank) to the no water washing 
stabilizing (first tank), the countercurrent system (two-stage 
countercurrent) was used, and similarly for bleach-fixing, from the 
bleach-fixing (second tank) to the bleach-fixing (first tank), the 
countercurrent system was used. 
The amount of the processing liquor carried over from the preceding tank of 
each tank was 0.6 ml/dm.sup.2. 
In the following, the recipes of the tank solutions and the respective 
supplementing solutions are shown. 
______________________________________ 
Color developing tank solution: 
Potassium carbonate 30 g 
Sodium sulfite 2.0 g 
Hydroxylamine sulfate 2.0 g 
1-Hydroxyethylidene-1,1-diphosphonic acid 
1.0 g 
(60% aqueous solution) 
Hydroxyethyliminodiacetic acid 
3.0 g 
Magnesium chloride 0.3 g 
Potassium bromide 1.2 g 
Sodium hydroxide 3.4 g 
N-ethylene-N-.beta.-hydroxyethyl-3-methyl- 
4.6 g 
4-aminoaniline chloride 
Made up to one liter with addition of water and 
adjusted to pH 10.1 with sodium hydroxide. 
Color developing supplementing solution: 
Potassium carbonate 40 g 
Sodium sulfite 3.0 g 
Hydroxylamine sulfate 3.0 g 
Diethylenetriaminepentaacetic acid 
3.0 g 
Potassium bromide 0.9 g 
Sodium hydroxide 3.4 g 
N-ethylene-n-.beta.-hydroxyethyl-3-methyl- 
5.6 g 
4-aminoaniline chloride 
Made up to one liter with addition of water and 
adjusted to pH 10.1 with sodium hydroxide. 
Bleach-fixing tank solution and 
supplementing solution: 
Ferric ammonium diethylenetriamine- 
0.5 mole 
pentaacetate 
Hydroxyethyliminodiacetic acid 
20 g 
Ammonium thiosulfate (70% weight/volume) 
250 ml 
Ammonium sulfite 15 g 
2-Amino-5-mercapto-1,3,4-thiadiazole 
1.0 g 
Aqueous ammonia (28%) 20 ml 
Made up to one liter with addition of 
water and adjusted to pH 7.6 with acetic 
acid and aqueous ammonia. 
No water washing stabilizing tank solution and 
supplementing solution: 
5-Chloro-2-methyl-4-isothiazolin-3-one 
0.01 g 
2-Methyl-4-isothiazolin-3-one 
0.01 g 
Ethylene glycol 2.0 g 
Ferric ammonium diethylenetriamine- 
0.03 mole 
pentaacetate 
Made up to one liter with addition of water 
and adjusted to pH 10.0 with aqueous ammonia 
and sulfuric acid. 
Stabilizing tank solution and supplementing solution: 
Formalin (37% aqueous solution) 
3 ml 
Konidax (produced by Konica Corporation) 
7 ml 
Made up to one liter with addition of water. 
______________________________________ 
Stabilizing processing was performed until the amount supplemented of the 
color developing solution into the tank became 3-fold of the color 
developing solution tank volume. 
The waste liquors of the above color negative film and the color paper were 
mixed at a ratio of 1:1 and used. 
EXPERIMENT 1 
In a disposal device, in which 10 ppm of hydrogen sulfide in the 
photographic processing waste liquor was set as the detection 
concentration in FIG. 2, the above waste liquors each individually and a 
mixture thereof were processed. As the result, fluidity of precipitates 
collected at the sludge receiver 6 in FIG. 2 is preferred and no clogging 
due to the precipitates at the part 1b in FIG. 2 is occurred. 
A processing time from initiating processing of the photographic processing 
waste liquor to stopping the processing by the set gas detection 
concentration is shown in Table 1. 
TABLE 1 
______________________________________ 
Processing time 
Kind of waste liquor 
(hour) 
______________________________________ 
Color paper 
Whole liquid 10 
mixing 
CD 25 
BF 5 
No washing 25 
stabilizing 
Color negative 
Whole liquid 10 
mixing 
CD 25 
BF 3 
No washing 25 
stabilizing 
Stabilizing 100 
Paper and negative 
10 
whole liquid mixing 
______________________________________ 
The processing times shown in the above Table 1 were just good times for 
processing the photographic processing waste liquor. 
EXPERIMENT 2 
In the experiment of the overall waste liquor of paper negative in 
Experiment 1, at the time of stopping of concentration processing, a 
solution of 200 g/liter of K.sub.2 CO.sub.3 and 100 g/liter of K.sub.2 
SO.sub.3 was added. As the result, the odor of the concentrate taken out 
after stopping was very little as compared with the case of no addition, 
and also the odor (H.sub.2 S) in the stored liquid was lowered from 3 ppm 
to 0.5 ppm, thus giving preferred results. 
EXPERIMENT 3 
In the experiment of the paper negative overall waste liquor in Experiment 
1, the experiments of liberating Epolion T (trade name, produced by 
Epolion Co.), Odridspray (trade name, produced by Biocheid Japan Co.), 
Kozoreclean (trade name, produced by King Kagaku Co.) and Freshraimatsh 
(trade name, produced by Shiraimatsu Shinyaku Co.) as the deodorant into 
the device. As the result, as compared with the case in absence of a 
deodorant, the odor was found to be lowered to greater extent, giving 
preferred results. 
The disposal device for photographic processing waste liquor of the present 
invention as described above has been made such that the evaporation 
concentration disposal is stopped by the control means when the gas 
concentration is detected by a gas detecting means to become a 
predetermined value, and therefore fluidity of the precipitates formed by 
evaporation concentration will not be damaged, whereby the precipitates 
obtained by evaporation concentration can be easily taken out without 
attachment on the inner walls of the evaporation means. 
Further, since control of stopping the evaporation concentration is 
performed by detecting the gas concentration, the control information for 
stopping the evaporation concentration can be obtained simply and surely.