JPH09299922A - Effective treatment of viscera of scallops - Google Patents

Abstract

PROBLEM TO BE SOLVED: To execute a treatment in a short time by removing harmful materials from polluting processed marine product waste, etc., and eliminating the malodors and waste water contamination generated by an active sludge method treatment in the treatment of the waste. SOLUTION: The waste of cadmium-contg. contents and other marine and livestock processed products is boiled and separated. The waste formed by solidifying protein in such a manner is filtered out. Fats and oils and the protein are recovered from the waste. Further, the filtrate is treated with active carbon fermentation humic acid and protein flocculating material, by which the filtrate is filtered. Further, the filtrate is adsorbed by ion exchange resins. Adsorption media are added together with enzyme to the filtrate to adsorb the filtrate. The clean liquid is subjected to dephosphorization and denitrification by water hyacinth, etc., and thereafter, the liquid is released. The recovered protein is subjected to cadmium removal by an electrolytic acid alkaline liquid and alcohol water and is subjected to adsorption and purification by the ion exchange resins. The recovered cadmium filtrate is neutralized and is then washed with water. The protein is dried and the pulverized protein is used as animal feed and food or as a soil improving fertilizer. The washing liquid of the filtration is purified by the adsorption treatment with the ion exchange resins, etc., and is released.

Description

Detailed Description of the Invention

This invention removes harmful substances from pollution-related marine product processing wastes and livestock processing wastes that have been conventionally incinerated or packed with concrete, and further, activated sludge method treatment that has been carried out in the treatment of these wastes is deficient. It improves the malodor and wastewater pollution that occur inside and coagulates the protein by boiling as a short-time treatment method, facilitating the separation of water and protein, and coagulating and precipitating the protein dissolved in water The coagulated product is easily filtered to prevent the reoccurrence of bad odors, and the cadmium heavy metal pollutants in the filtered filtrate are treated with a flocculant using an ion exchange resin or activated carbon humic acid fermenting material and adsorbed and purified. Is adsorbed by radiative calcium and zeolite ceramics, discharged dehydrogenation and nitrogen separation decomposed by aquatic plants and decomposing enzymes, and further, the solidified product obtained by separation of boiled and coagulated protein by an electrolytic membrane, Lucari water and the filtrate separated by the electrolytic membrane are neutralized, and harmful metal ions are adsorbed and removed by treatment with ion-exchange resin, activated carbon humic acid ferment and iron sulfate, and the filtered wastewater is adsorbed with calcium zeolite ceramics. ,
When it is treated with aquatic plants, dephosphorylated, and discharged, B. O.
D is reduced to one half of the known value, and the treatment time is 12 hours by the activated sludge method, but it has the advantage of being treated within about 1 hour, and it is decomposed like proteins and oils and fats. As a result of the short-time treatment of wastes that tend to give off a bad odor and the sterilization method of boiling, there is an advantage that a secondary bad odor does not occur, and even when bonito blood water is drained, protein coagulation by heating facilitates the separation of protein blood. Since the odors of contained hormones and degrading enzymes can be easily separated, the diffusion of odors due to the blast in the conventional activated sludge method is prevented, so there is no secondary pollution, and there is no marine pollution or river pollution. The concentration of excess phosphoric acid and nitrogen compounds can be easily regulated by the release to the river, and it can be effectively used for the treatment of blood water in livestock processing. In particular, when boiling protein sludge and scum cake in sausage processing, it prevents odorous factors, and it is not necessary to install a gas tank or a concentration tank. This is because the protein is easily separated from water by heating and coagulation and hydrolysis of the protein is stopped by sterilization, so that there is no bad odor, and the transparency of the drainage is as good as 10 m. In addition, in the electrolysis, when sodium sulfate is used as the electrolyte by performing diaphragm electrolysis, the sulfuric acid solution 10 is used as the anode.
%, A caustic alkali solution is made at the cathode, and when a hollow chamber is made with this electrolytic diaphragm, a neutral solution is obtained and the alcohol-alkaline solution of the protein coagulated therein is obtained. When placed and electrolyzed, cadmium concentrates in the cathode chamber for decomposition and purification. Then, neutralization with the anolyte facilitates adjustment of the PH value. Also, electrolysis of this anode with an iron electrode produces an acidic solution of iron sulfate, and when this iron sulfate is added to the activated carbon fermented humic acid solution and heated, things such as blood water also agglomerate and settle, and the bad odor is absorbed and deodorized. The effluent is purified because a clear liquid is produced.To remove cadmium and heavy metal harmful substances in the effluent during this treatment, the cadmium is recovered and adsorbed when the ion exchange resin is used for purification. There is almost no pollution of cadmium in the wastewater. or,
Radiation calcium, zeolite 30%: 70%
Mix the mixture in the proportion of calcination temperature of 800 ℃ and put the phosphorous rods and pellet spheres in the tank, and immerse the wastewater in the tank containing Aspergillus bacterium, proteolytic enzyme, and lipase for adsorption. Since it is also decolorized at the same time, it changes to clear wastewater and soluble oil and fat decomposition products in the water solution are also removed, but since phosphoric acid solution, sulfuric acid solution and nitrogen compound solution remain in this wastewater, these Ammonia, which is a nitrogen compound that is absorbed by the roots of aquatic plants and dephosphorylated, reacts with sulfuric acid to become ammonium sulfate, so that the roots are easily absorbed. O. D is 1P. P. It is released to the extent of M and has no pollution. If the wastewater contains a large amount of phosphoric acid, ammonia, saline, or sulfate, it is not harmful if it is electrolytically removed by placing it in the inner chamber of the diaphragm electrolysis. In this way, the treatment method of the present application is a treatment method that takes a long time for decomposing water vapor in the processing of fishery products and livestock products that are constantly suffering from bad odor pollution. It does not have a bad odor because it is separated in 60 minutes and the separation of fats and oils is done at the same time. However, the internal organs boiled with simple iron-tin are odorless when they are immediately processed before being decomposed or proteolytically decomposed. However, it is not easy to separate proteins from toxic substances such as cadmium, which is a pollutant, and proteins are chelated, and since the permeability of the treatment chemicals is poor, the separation is rather acid. The method of alkali extraction is easy. The recovered fats and oils are hydrogenated and used for cosmetics and foods.
Since protein is used for feed and fertilizer, its processing cost is 5
It has a feature of covering 0 to 80%, and since the transparent liquid can be seen even at 10 m, it will be an improvement in future water treatment methods. Further, because of the harmful cadmium, especially when the cost of the scallop's internal organs is incinerated and replaced by boiling, the fuel consumption is halved, which is an industrially useful invention.
The embodiment of the present invention will be described below with reference to the drawings.

FIG. 1 shows a process diagram for processing fishery processing and livestock processing. First, cultured scallops are collected (4b) and separated into shells (1a), scallops (1c) and offal (1b). ), The separated shell (1a) is washed with water, dehydrated (3a), fermented and decomposed (3'a), crushed (4a), sorted (5a) and used as a purifying agent (6a). . The offal (1b) is taken from the scallop scallop (1c), and the scallop (1c) is washed separately with water and dehydrated (2c), which is then frozen and stored as frozen food (3c) before being packaged and shipped. The internal organs (1b) are washed with water and boiled in a boiling tank (2
It is put in b) and heated with steam at 90 ° C. or higher, and the supernatant liquid is pumped up and applied to the oil-water separator (3b) to separate the oil and fat (4b), and the filtrate (5b) is sent to the next treatment. The heat-coagulated product of 1b) is placed in a separator, dehydrated (6b), and placed in a grinder (7'b) to be ground to enter a cadmium-free process.
this is,

[Fig. 2] The protein is immersed in the alkaline solution tank (4E) of the electrolyzer shown in Fig. 2 and cadmium ions are made to be protein (4E) to be liberated, and separated by a separator (3E) to obtain a filtrate (3'E). Separated into alkaline protein (6E),
E) is

FIG. 4k is a three-chamber electrolyzer and put in a medium-quality (10F) electrolytically refined (7E) electrode (4F) (4′F) to carry out dealkalization. These alkali ions and cadmium ions move to the cathode chamber, and the neutral chamber (10F) becomes neutral, so that electrolytic refining is performed. The alkaline water and the cadmium water thus separated are separated (9E) by a separator, the filtrate is neutralized by a neutralizer (13E), treated with an ion exchange resin (15E), and decadmized. The liquid (15'E) is pumped to the adsorption purification tank and combined with the purification liquid for use.
At this time, the separated protein (10E) was washed with water (12
The protein E), neutralized with acid (13E) and washed with water, is processed with a vacuum dryer (18E) from a heating tank (17E) to make a dried protein (21E). The water liquid (15'E) formed at this time is mixed with the fermented wood fiber (19E) and the bacterium to be fermented in the fermentation chamber to have a water content of 80% to produce an organic fertilizer (20E). On the other hand, dried protein (21E) is mixed with the compounded feed (22E) at 30% to make a protein feed. It has no cadmium. Next, the filtration liquid (6b) is adsorbed and decolorized (7'b) by adsorption purification Tanac (7b) containing activated carbon humic acid to purify the water liquid, and then filtered (8
It is treated with b) and separated from the solid adsorbent (9b), and this solid adsorbent is filtered and regenerated by heating at 400 ° C. This filtrate (10b) was introduced into the next adsorption purification tank (11b) by a pump, and a firing rod (11'b) containing a mixture of radiative calcium and zeolite at a ratio of 20:80 was placed in the tank (11b). After about 10 minutes, the liquid was treated with a filter (12b) to obtain the filtered liquid (13).
In b), decadmium is removed by an ion exchanger (14b) to prepare a decadmium liquid (15b), which is mixed with water (18b) and discharged (17b). The wastewater discharged during this process is sent to the adsorption purification tank (11b) and is adsorbed and purified to be successively purified. The cadmium in the wastewater at this time was 0.
There is no pollution at 001% or less. Further, the content of cadmium in the deproteinized protein is reduced to 0.002%. Even when this scallop waste is mixed with the waste of other processed marine products, if it is heated in the same manner to coagulate the protein, the malodor in the subsequent steps is prevented. That is, since the decomposition method by the oxidative-decomposing bacteria in the publicly known waterfall tank is decomposition at room temperature, even if the electricity for the decomposition is blown, the B. O. D is 1000P. P.
It takes 12 to 20 hours to decompose the sewage of M, and there is a drawback that the amount of scum rake is not decomposed below a certain level. During that time, there is bad private pollution, but if the boiling method is adopted, it will be 1 at 90 ° C.
The protein coagulates in 0 to 15 minutes, and the degrading bacteria causing the malodorous substance disappears, so that the next generation of malodorous substance is small. Further, the malodor of the oxidized fat is deodorized by hydrogenation to obtain a saturated fatty acid. The rinsing water generated in each process is treated with activated carbon humic acid, adsorbed and purified with ceramics, and further dephosphorized and denitrified with aquatic plants to release pollution-free wastewater. O. D is 1
P. P. It is released at about M. In addition, the sewage treatment of sausage processing may cause the sludge of animal protein to reach 1 to 3%, and when fermented and decomposed, the foul odor becomes more and more intense due to the generation of organic acid. Therefore, the sludge obtained by the screening is also boiled. When the protein coagulates, the odor is prevented.
In addition, since blood is coagulated by boiling bonito-processed blood water drainage, separation of water and protein becomes easy. In slaughterhouse effluent, a large amount of hormones, viscera, proteolytic enzymes pepsin, trypsin, lactic acid, valeric acid, and other malodorous substances and manure are contained in the internal organs. Mix Aspergillus and papaya enzyme into
When the process of fermenting at ℃ is introduced, the malodor immediately disappears at a ratio of 1: 1. Therefore, when sewage is also adsorbed on this fiber and fermented at a fermentation heat of 80 ℃, sewage evaporates and decomposes, so it is recommended to use it together. Further, in the case of general activated sludge method treatment, a huge water tank requires a huge area, but in the boiling method, about 1/10 is sufficient. Sewage in a fish processing plant B. O.
D is about 4000P. P. Since it is M, and the processed fish debris can reach 10 ton / day in the processed complex, the boiling method has a feature of being useful for resource recovery.

FIG. 2 is a side view of a diaphragm electrolyzer in which an electrolyte solution, sodium mirabilite (2F), is placed in an electrolytic cell (1F) of a diaphragm (3F). The cathode chamber (W) and the anode chamber (V) are shown in FIG. 50 glauber's salt solution was added
~ 60 volts 0.1-1 ampere power (4
F) When applied to the cathode (4'F), the anolyte compartment liquid is acidic,
Since the cathode chamber becomes a caustic liquid of alkaline liquid, it is transferred to these acidic water storage tank (8F) and alkaline water tank (8'F), and this is used as a decadmium immersion liquid after boiling of scallop internal organs, Acidic water and iron sulfate solution are used as neutralizing and coagulant solution. The amount of reduction of both liquids in the anode and cathode chambers is
F) An inexpensive method of replenishing from (6′F) and adjusting to a certain level is performed by utilizing the capillary absorption effect of fibers.
The acidic liquid and the alkaline liquid have been described above.

FIG. 3 shows a side view of the diaphragm electrolyzer, showing the cathode chamber (U).
Alkaline electrolyzed water is added, a small amount of alcohol solution is added, and an alkaline water solution is also added to the anode chamber to make the anode chamber alkaline and electrolyze. A basket is placed in the anode chamber (W) and the cathode chamber (U), and crushed granules of boiled protein are put into the inside of the basket to electrolyze, and the basket in the anode chamber (W) (9F)
In the inner protein boiled granules of (9′F), cadmium ions move to the cathode chamber through the diaphragm by the alkaline liquid in the anode chamber, and the alkaline liquid in the cathode chamber is liberated from the protein by increasing the alkali ions and cadmium ions. This is put on a dehydrator and filtered, and the dehydrated protein granules are collected and washed with water.

FIG. 4 shows a basket (9) in the central chamber (10F) of the three-chamber diaphragm electrolyzer.
FF) Insert the solution into the anode chamber (W) and the cathode chamber (U) with neutral water as an electrolytic solution, and put 1 to 3% of thin sodium sulfate water into the anode chamber (U) and electrolyze at 50 volts and 0.1 amperes. Since it becomes an acidic liquid, the cathode chamber becomes an alkaline liquid, and the neutral liquid in the middle chamber becomes a thin acidic Glauber's salt solution, so when alkaline water is added to make it neutral, the cadmium-containing ion is released into the cathode chamber, Cadmium adsorbed on this liquid with an ion exchange resin is recovered. At that time, the cadmium in the protein is gradually released into the central chamber (Z) of the neutral solution or the alkaline solution, and the concentration thereof is gradually reduced, so that it is used for decadmium. The decadmium-depleted protein granules are dehydrated by withdrawing a basket (9FF), washed with water, dehydrated with a dehydrator, and dried under vacuum to be used as a feed material and a fertilizer material. The amount of recovery depends on the fish processing complex, but in the case of Tottori, 500 kg to 1200 kg / month of decadmium processed products can be obtained. Fats and oils are about 300 kg. As a result, the cost required for boiling is covered by a part of the sales, and the cost is considerably reduced as compared with the conventional method using the activated pollution method. If only scallops are used, it can be considered to be used as a purification agent for shellfish, but if it is carried out at the same time as the waste from the miscellaneous seafood processing plant, the amount of feed and fertilizer raw materials used will be mass-produced, which is highly economical. In addition, in the generally known activated sludge method, first, the sludge is screened to remove the sludge and the sludge is treated as industrial waste, and the scum cake of the sediment of the wastewater is further filtered by dewatering and collected. It is a costly task that must be treated and, in addition, the malodorous gases produced during oxidative decomposition in a moist tank are a problem with air pollution due to incomplete prevention. Therefore, in order to solve these problems, it can be solved only by the boiling method, and by the further purified activated sludge method, B. O. D is 20P. P. Although the range below M is the limit range, it is difficult to purify soluble substances such as blood water, which can be solved by adopting the boiling method and the adsorptive decolorization method. O. D is 1P. P. It falls below M.
This heating is also performed at night without electric power by using an electric boiler and a cooker heating can, and a series of treatment steps are performed within 60 minutes. Also, in the case of leather with the conventional method of incineration in an incinerator, cadmium not only partially remains in the ash and the other volatilizes to cause air pollution, and it is necessary to perform a secondary treatment of the ash. There is. When heavy oil is used for heating in the present application, the amount of consumption is 300 kg / ton of heavy oil / day, but in the case of incineration, the amount of consumption is 2-3 ton / ton. This has the drawback that the furnace is repaired once every three months in order to incinerate industrial waste with a water content of 85% to 90%. Further, there is a drawback that the problems of resource utilization and pollution cannot be solved, and the generation of toxic chlorine compound gas due to salt must be solved.

FIG. 5 shows a process diagram of wastewater treatment. Boiled marine wastes are separated into oil and fat by oil-water separation air (2S) and stored in a tank (3S), and the wastewater after recovery is decadmized with an ion exchange resin vessel (4S) to obtain acid-alkali Wash with and collect the washing liquid to collect cadmium. next,
The decadmium wastewater that has passed through the ion exchange resin is introduced into an autoclave (6S) by a pump (5S), fermented fiber humic acid iron sulfate activated carbon (K) is placed in a basket (7S), heated and adsorbed at 70 ° C. Then, after adsorbing while stirring with a stirrer (8S) for about 30 minutes, the drainage was processed into an autoclave (9S) into a rod-shaped radiation calcium carbonate 20.
% Zeolite 80% was masticated with 20% polyvinyl alcohol water and extruded with an extruder to nourish the rod. The rod was dried and singulated, and heated and calcined at 800 to 900 ° C. for 4 hours to 10 hours. The adsorption rod (OS) of the kneading rod is inserted into the autoclave (9S) and the industrial waste is introduced into the autoclave for adsorption treatment, and proteolytic enzyme and other soil bacteria are put on the upper portion to adsorb at 60 ° C for decomposition. Close. This supernatant liquid is transferred to a hydroponic tank (13S) through a pipe (12S), and phosphate ions, ammonia, and nitrogen compounds adsorbed by Hotei grass (14S) are mixed with water, diluted and discharged. .
B. of this drainage O. D is 1P. P. It becomes M or less. This hot water grass (14S) is collected from the water surface with a net, crushed with a crusher (15S), and then fermenter (17S) (17'S) with a mixer (16S) to remove bark, sawdust, and leaf plant fibers. (18S) (18'S) is mixed with Aspergillus bacterium, and Aspergillus bacterium (100 million strains is adsorbed) per 1 g of the mushroom powder adsorbed on zeolite powder, and ground product of Hotei grass (14S) is mixed, Fermented humic acid fiber (7S ') decomposed by fermenting at 40-60 ° C with a water content of 80% is 60-90.
The fermented product that has been allowed to stand for a day is put into an autoclave (6S) for adsorptive decolorization together with activated carbon (7'S) in a basket to purify wastewater. This activated carbon burns humic acid at a temperature of 500
It is produced by heating and carbonizing at ℃ to 600 ℃, and then blowing steam at 1200 ℃ to burn. Further, the recovered oil / fat tank (3S) is sent to an autoclave (3 ′S) to mix 1 to 3% of a reduced metal catalyst of nickel and cobalt by hydrogen carbonization at a pressure of 30 to 100 kg to obtain a saturated oil and fat. If the fat is an old material that has been oxidized, it is refined with caustic water to neutralize it. Activated carbon 50kg + in this wastewater treatment
50 kg of fermented humic acid fibers and 50 g of iron ore are put in a bag and put into an autoclave (6S) to perform an adsorption action. After this treatment, odors etc. are removed and the effluent has a transparency of 1
However, it is decomposed by the action of a fermentation enzyme due to adsorption by a radiative calcium and a zeolite firing rod, and the amount of 1P. P. It becomes M. As described above, the feature of the present invention is that the activated sludge method, which has been widely put into practical use in the past, is about 4 to 1 ton of waste in processing of marine product processing waste and livestock waste.
It is necessary to use water of 0 ton for a period of 6 to 10 hours, and the supernatant after warming is added to B.I. O. D5-20
P. P. It takes 40 to 60 ton of water to decrease to M. O. D5-20P. P. In contrast to M, the boiling method of the present invention uses 2 tons for 1 ton of waste.
The addition of n water is sufficient. This is because the water-soluble and easily hydrolyzable protein is solidified by heating to form a clear solution in 20 to 30 minutes, and the protein precipitates. Therefore, oil and fat are removed from this clear solution and activated carbon, fermented humic acid and a small amount of it are removed. When heated with iron sulfate, ammonium sulfate, light vane, etc., water-soluble fats and oils are completely precipitated and adsorbed, and deodorization and decolorization are also performed.The transparency is still yellow water in the activated sludge method. What is present is B. O. D5-20P.
P. In the case of M, the addition of this activated carbon-fermented humic acid and salts made it almost colorless. O. D1P. P. Purified to below M,
When this is further adsorbed with the enzyme using a radiative calcium zeolite firing rod, soluble amino acids are also adsorbed and removed. And B. O. D is 0.5 to 0.8
P. P. It becomes as low as M, and there is no harmful bacterium due to the rapid heat treatment, and it becomes complete river discharge water. However, since nitrogen compounds such as ammonia and phosphates are present in this purified water, absorption by these aquatic plants not only causes a factor of red tide, but also because aquatic plants grow early, this aquatic plant becomes secondary pollution. When it is mixed with fermented fiber and decomposed with Aspergillus to make fermented fiber, it is useful for the growth culture of fermentative bacteria, the fermented fiber can be recycled, and the fertilizer is also produced with the fermentation of the waste protein. It can also be used.
In particular, when processing an excessive amount of protein waste in a fish processing complex or a livestock processing factory that processes marine products other than scallop processing, it is also effective in preventing foul odor pollution. Then, the protein waste produced by the main boiling method is filtered and added to the feed to make a compound feed, which is used for chicken, cow, pig, and
Since it is used as a feed for cultured fish, it is possible to effectively use the scum cake, which cannot be used for a secondary purpose like sludge in the general activated sludge method. Moreover, since cadmium can be removed from internal organs containing a large amount of cadmium, such as scallops, the internal organs that have been incinerated can be effectively used.
Also, in the treatment of waste in markets and super food processing plants, for example, in the treatment of bulky vegetables, bulkiness is prevented by the boiling method, and malodor is prevented by mixed fermentation with fermented fiber. Reduce pollution. With this malodorous gas, fermented fiber may be treated at a ratio of 1: 1. Also in the cadmium treatment, heat treatment facilitates crushing and extraction, and refining by the electrolytic method can reduce the cadmium content to 0.001% or less, which is industrially useful. It is an invention.

[Brief description of drawings]

[Fig.1] Process drawing of scallop collecting

FIG. 2 Side view of an acid-alkali membrane electrolyzer

FIG. 3 Side view of diaphragm electrolyzer

[Figure 4] Side view of electrolyzed products

FIG. 5: Process diagram of boiling method

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C02F 3/32 C02F 3/32 // A23L 1/325 A23L 1/325 C

Claims (1)

[Claims] As described later, the contents of cadmium containing scallop scallops and other marine and livestock processing wastes are first boiled to separate oils and fats, and the proteins are coagulated to prevent the subsequent generation of a bad odor. The oil and fat are recovered by separating the oil and protein, and the filtered solution is treated with activated carbon fermented humic acid and a protein coagulant to be filtered, and the filtered solution is adsorbed with an ion-exchange resin to produce a radiative marble. Zeolite is adsorbed by adding it with a calcined adsorbent together with an enzyme, and the purified solution is dephosphorized and denitrified with watery grass, aquatic plants, etc., and then discharged. Recovered protein is cadmium deoxidized with alkaline solution of electrolytic acid and alcohol water. After neutralizing the decadmium filtrate that has been adsorbed and purified with an electrolytically purified ion-exchange resin, it is washed with water and purified, and the protein is dried in a vacuum dryer and powdered into animal feed or food. As well as the soil Utilized as an improved fertilizer, its filtered off washing liquid ion exchange resins, activated carbon humic acid, calcium,
An effective treatment method for the processing and utilization of marine product processing waste and livestock processing waste, in which it is adsorbed by zeolite ceramics moldings, enzymes, aquatic plants, etc. and purified before being discharged.