JPH0553521B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a flocculant, and more particularly to an animal bone-containing flocculant that is particularly effective for flocculating organic matter in treated liquids such as wastewater, and methods for producing and using the same. (Prior art) Bando sulfate, aluminum chloride polymer,
Ferric chloride etc. are present. On the other hand, the conventional method for treating wastewater containing organic matter has mainly been an activated sludge method. The activated sludge method allows microorganisms such as bacteria to grow, thereby adsorbing organic matter in the sludge and separating impurities by sedimentation, and has a high purification ability.
Water treated by the activated sludge method was discharged directly into rivers, etc., as long as it met certain water quality standards. (Problem to be solved by the invention) However, since all of the above conventional flocculants react on the acidic side, the treated water must become acidic, and the problem of environmental pollution due to discharge remains. Ta. Moreover, the above-mentioned flocculant did not react with general public tap water or water with a low degree of contamination, but functioned with considerably contaminated wastewater. In view of the above, the present invention prevents the risk of environmental pollution due to discharge of treated water by reacting in a neutral or alkaline range, and has high reactivity that reacts with ordinary public tap water or water of the same level. It is an object of the present invention to provide a flocculant that has the same properties as conventional flocculants and exhibits sufficient functionality with an extremely small amount used compared to conventional ones. On the other hand, in the conventional activated sludge method, when wastewater containing putrefactive organic matter such as animal products is treated with this activated sludge method, the quality of the treated water obtained by this method satisfies the standard value that can be discharged. In Although,
PH is acidic, BOD and COD are both around 30 to 60 ppm,
The water quality could not necessarily be said to be sufficient in terms of being harmless to natural water bodies, such as odor not being completely removed. Moreover, the above-mentioned treated water was not suitable for reuse as factory water, washing water, or the like. Furthermore, it is necessary to maintain conditions such as keeping the activated sludge tank at a temperature of 20 to 30 degrees Celsius where microorganisms can reproduce, as well as constant aeration to supply oxygen and the presence of an appropriate amount of organic matter. , the processing time was quite long. Further, complex and large-scale equipment is required, and the equipment cost is large, and maintenance costs and labor are also excessive. Therefore, unlike the conventional activated sludge method that uses microorganisms such as bacteria to separate impurities from wastewater, the present invention can be used as a simple means of setting conditions, and is easy to use and maintain on a small scale. This method deodorizes, sterilizes, and purifies wastewater, especially wastewater containing putrefactive organic matter such as animal matter, in a short period of time, producing recycled water with a quality equal to or better than that of tap water, and does not cause pollution even when released into natural water bodies. The purpose of the present invention is to provide an animal bone-containing flocculant particularly suitable for wastewater treatment, which not only does not pose a risk of wastewater, but also produces reclaimed water suitable for wide-scale reuse, thereby enabling efficient wastewater treatment. It also has. (Means for Solving the Problems) In order to achieve the above object, the present invention was made by focusing on animal bones that have adsorption properties and are ionized into alkali. An animal bone-containing flocculant consisting of an osteolytic solution obtained by dissolving ground animal bone powder in sulfuric acid or hydrochloric acid, and an osteolytic solution obtained by dissolving calcined and powdered animal bone powder in sulfuric acid or hydrochloric acid, Alternatively, there is an animal bone-containing flocculant that is uniformly mixed with a metal solution dissolved in hydrochloric acid. In addition, a bone solution is obtained by mixing calcined powdered animal bone powder with sulfuric acid or hydrochloric acid, and a metal solution is obtained by mixing iron or copper with sulfuric acid or hydrochloric acid, and then both solutions are mixed. A method for producing an animal bone-containing flocculant, characterized in that the animal bone-containing flocculant is made of an osteolytic solution obtained by dissolving calcined and powdered animal bone powder in sulfuric acid or hydrochloric acid. A method for using an animal bone-containing flocculant, which is characterized in that the animal bone-containing flocculant is used after adding an alkaline reactive material to a treatment solution, and an osteolytic method in which calcined and powdered animal bone powder is dissolved in sulfuric acid or hydrochloric acid. An animal bone-containing flocculant, which is a uniform mixture of a liquid and a metal solution prepared by dissolving iron or copper in sulfuric acid or hydrochloric acid, is used after adding an alkaline reactive material to the treatment liquid. Methods for using animal bone-containing flocculants. In the above manufacturing method, calcined and powdered animal bone meal is mixed with sulfuric acid or hydrochloric acid at a ratio of about 1 to 1.5 of the latter to about 1 kg of the former to dissolve the bone powder,
After that, it is diluted with water and filtered to obtain a bone solution.Meanwhile, iron or copper and sulfuric acid or hydrochloric acid are mixed at a ratio of about 1 to 1.5 per about 100g of the former to dissolve the iron or copper, and then diluted with water. and filter to obtain a metal solution, and then combine the above bone solution and metal solution,
It is preferable to have a step of mixing and homogenizing the former at a volume ratio of about 0.3 to 0.7 to the latter. (Function) Animal bone meal has the effect of alkalizing the atmosphere with its components, such as calcium ions, and coagulating organic matter. Dissolved metals such as copper are easily compatible with organic substances and have reactivity, and have the effect of coagulating the organic substances more firmly and adding weight to cause the aggregates to settle. (Example) (1) About the animal bone-containing flocculant The animal bones used as raw materials for the flocculant of the present invention are bones that have conventionally been mostly discarded at livestock farms, especially the hard bones of cows, horses, sheep, etc. Animal bones are used. The bones of pigs, boars, etc. have a lot of cartilage, and most of them melt during the boiling process during production, so they are not suitable for use as raw materials. The above-mentioned raw bones are cut into appropriate sizes and cut into sizes that are easy to burn, and then placed in a pressure cooker (compression cooker) at a temperature of about 90℃ at around 200-400℃.
Boil for a minute or so. Next, the bone is placed in a firing furnace and fired at around 900 to 1100°C for about 60 to 180 minutes, and then allowed to naturally cool in the furnace for around 60 minutes to return to room temperature or a state close to this temperature. Gelatin, fat, white matter,
If organic matter such as glue remains, it will cause oxidative decay, so it is important to ensure that it is removed. By the above-mentioned boiling process, most of the organic matter adhering not only to the outside but also inside the pores can be separated and removed from the bone. At this time, if the boiling is done at a lower temperature or for a shorter time than the above, the organic matter cannot be removed sufficiently, causing problems in the subsequent firing process. There is no advantage to using boiling conditions at a higher temperature or for a longer time than the above. In this way, by removing most of the organic matter in the boiling process and then passing through the baking process, the remaining organic matter can be completely removed, and at the same time, the humidity (moisture) in the bone can be reduced to preferably a few percent or less. can be reduced to almost 0%. Firing without a boiling step is not preferable because it causes significant combustion of organic matter and smoke generation, resulting in environmental pollution, discomfort during work, and damage to equipment. If the firing conditions are clearly lower than the above,
The bones will become carbonized, and if the temperature is too high, the bones will turn to ash, and in either case, the object will not function as intended by the present invention.
According to the above conditions, the bone becomes white and maintains its original state with numerous pores. After the above-mentioned firing and cooling, the bone is crushed and passed through a powder machine to obtain bone powder of approximately 20 to 200 meshes. In the case of bovine bones, the yield of the above-mentioned bone meal was approximately 40% by weight compared to raw raw bones. The particles are mainly composed of calcium, phosphorus, magnesium,
It is made of barium, sodium, sulfur, potassium, aluminum, iron, zinc, copper, nickel, etc., and has countless microscopic pores that communicate between the inside and outside of the particle. Ionization is alkaline due to calcium etc. The above bone powder and sulfuric acid are mixed at a ratio of about 1 to 1.5 of the latter to about 1 kg of the former, and the bone powder is dissolved over about 2 hours (or more), resulting in a mixture of about 8 to 12 times the ratio of the sulfuric acid. After diluting () with water, this is filtered to obtain osteolytic solution A. Note that hydrochloric acid may be used instead of sulfuric acid, but
When mixed with a metal solution to be described later, sulfuric acid is preferable in terms of its efficiency in dissolving iron or copper. The animal bone-containing flocculant of the present invention can be prepared by using only the above-mentioned osteolytic solution A. On the other hand, add iron or copper and sulfuric acid to 30 to 60 g of iron and 40 g of copper.
Mix the latter at a ratio of about 1 to 1.5 to ~70 g of the mixture, and dissolve the iron and copper over about 24 hours (or more), to a ratio of about 8 to 12 times the sulfuric acid ()
After diluting with water, this is filtered to obtain metal solution B. In addition, iron and copper are reactive with organic substances,
It has the function of further promoting coagulation and adding weight to aggregates to make them easier to settle. Copper is more effective, but for economical reasons it is better to mix it with iron. Next, the above-mentioned osteolysis solution A and metal solution B are mixed at a volume ratio of about 0.3 to 0.7 of the latter to 1 of the former, and in order to make the mixing uniform, the mixture is heated at 80 to 120°C, preferably around 100°C. Boil for around 30-60 minutes,
Thereafter, the animal bone-containing flocculant of the present invention can be obtained by filtration. Since the aggregate, which is the main material of the flocculant, is alkali ionized, any of the animal bone-containing flocculants mentioned above reacts effectively in the neutral to alkaline range. Therefore, when using this for wastewater, etc., it should be neutralized or alkalineized (7.0
~9.5, preferably 7.0 to 8.5), at the same time as the flocculant, an alkaline reactant such as caustic soda or nitric lime is mixed into the wastewater at a ratio of about 0.3 to 0.7 of the latter to 1 volume of the former. It is best to use it as If the wastewater has a high pH of 9.5 or higher, use an acidic reaction material such as dilute sulfuric acid. However, since domestic wastewater contains a considerable amount of salt, calcium, etc., the reaction can be sufficiently promoted without the addition of the above-mentioned reactants. (2) Regarding wastewater treatment using an animal bone-containing flocculant Next, an example of a method and an apparatus for treating wastewater using the animal bone-containing flocculant of the present invention will be explained based on the drawings. FIG. 1 is a flowchart of a treatment process suitable for treating wastewater from ordinary households, factories, and the like. The device has an animal bone-containing flocculant tank 1, a reactant (caustic soda, nitric lime, etc.) tank 2,
The wastewater is first injected into a measuring tank 3 for adjusting the amounts of the coagulant and reactant added, and then flows into the stirring tank 4 where the reactant and animal bone-containing coagulant are mixed in and thoroughly stirred by a stirrer. Then, the organic matter is flowed under pressure into the pressurized flotation tank 5 by a compressor to coagulate and float the organic matter. The stirring tank 4 may be divided into a flocculant mixing tank 4a equipped with a stirrer and a flocculation reaction tank 4b equipped with a stirrer. The treated water passes through a skimmer disposed at the upper part of the pressurized flotation tank 5 and flows into a filtration tank 6. The aggregates floated under pressure in the pressurized flotation tank 5 are separated by a skimmer and then sucked into a sludge tank, where they are deposited as sludge. The filter tank 6 may be a layered layer of fine sand, which is made by kneading small pieces of animal bones calcined by the method of the present invention or pulverized animal bones and clay powder into granules. It may also be a stack of animal bone-containing granules that have been oxidized and fired. The former filtration layer can remove fine impurities after organic matter has been removed, so it can be used satisfactorily for general wastewater. The latter filtration layer not only removes the impurities, but also alkalinizes and mineralizes the treated water by alkali ionization of the bones, so it is particularly effective for wastewater with a relatively high degree of organic contamination. The above-mentioned treated water is tasteless and odorless, and there is no risk of environmental pollution even if it is discharged as it is, and it can be fully reused as water for washing or the like. Furthermore, if a mechanism is adopted in which the treated water is forced to flow back into the filtration tank through a separate pipe, automatic cleaning of the inside of the filtration tank is possible. FIG. 2 is a flowchart of a treatment process suitable for treating highly contaminated wastewater containing perishable organic matter, such as slaughterhouse wastewater, livestock processing plant wastewater, filth wastewater, and the like. First, wastewater discharged directly from slaughterhouses, etc.
The water is introduced into the adjustment tank 11 through an automatic screen, where large-particle impurities such as solids are removed and stored (hereinafter referred to as wastewater).
The wastewater passes through a measuring tank 12 that adjusts the flow rate and flow rate that can be processed per unit time, and then passes through a mixing tank 13.
It is introduced into the reaction tank 14. Both tanks are equipped with stirring blades, and are also connected with a reactant injection device 15 such as caustic soda or nitric lime, and an animal bone-containing flocculant injection device 16 according to the present invention, so that the pH of the wastewater can be adjusted. The reactant is injected to be within the range of 7.0 to 9.5, and a very small amount of animal bone-containing flocculant is added to the wastewater depending on the concentration of the wastewater (using the biochemical oxygen supply BOD as the measurement standard). Injected. For example, wastewater with a BOD of about 8001
Approximately 25 c.c. of animal bone-containing flocculant is injected into m ³ and mixed by stirring for approximately 1 to 5 minutes. The wastewater is then introduced into the pressurized flotation tank 17 from below under pressure by a compressor, and the aggregates that floated to the top due to the pressure are separated by a skimmer disposed above, and then Second reaction tank 1
It will be leaked on 8th. The aggregates floating upward and separated by the skimmer are discharged to the sludge thickening tank 31. The second reaction tank 18 is again injected with the required amount from the animal bone-containing flocculant injection device 19 and the reactant injection device 20 as necessary for pH adjustment, stirred and reacted, and then transferred to the coagulation sedimentation tank 21. The remaining organic matter that could not be completely separated in the pressurized flotation tank 17 is condensed and precipitated. The precipitate is discharged to the sludge thickening tank 31. After the treated water passes through a filter and is temporarily stored in a liquid storage tank 22, it is transferred to a vertically long filtration tank 23 in which sand is layered as a filter medium.
The liquid is transferred at a constant flow rate to flow down the filter tank 23 by gravity, and then stored in the liquid storage tank 24. 25 is animal bone obtained by kneading and granulating fine pieces of animal bone baked by the method according to the present invention as a filter medium, or bone powder obtained by turning the animal bone into powder, and clay powder obtained by baking clay as a binder into howder. This is a vertically long filtration tank made of layered main particles. The treated water in the liquid storage tank 24 is transferred to the filtration tank 25 at a constant flow rate, flows down naturally, receives addition of ClO ₂ from the sterilizer 26, is sterilized, and is stored in the treated water tank 27. Each of the filtration tanks 23 and 25 is for removing residual minute impurities, and the filtration tank 25 also has the function of alkaline ionizing the treated water using bone components such as calcium to turn it into mineral water. A backwashing blower 28 is connected to the treated water tank 27 via piping, and the treated water is forced to flow back into both the filtration tanks 23 and 25.If the treated water flows back into the filtration tank and is provided with a function for cleaning, the filtration tank can be cleaned. can be maintained over the long term without deteriorating function. Furthermore, a reclaimed water pump 29 is connected to the treated water tank 27 via piping, so that the treated water can be reused as washing water for slaughterhouses, etc. There is no risk of environmental pollution even if it is released as is. In addition, when the above-mentioned apparatus according to the present invention is combined with a wastewater treatment facility using a conventional activated sludge method or the like, the treated water discharged from the final settling tank of the conventional apparatus 30 is introduced into the second reaction tank 18, and the subsequent It is better to allow it to pass through a processing step. After the sludge accumulated in the sludge thickening tank 31 is concentrated, it is subjected to a sludge treatment process, excessively dried, and disposed of as appropriate, or it is subjected to a granulation process, then allowed to naturally ferment, and used as fertilizer or soil improvement material. can do. Since the sludge is a deposit of the organic matter, it exhibits excellent efficacy as a natural fertilizer or soil conditioner. Experimental example 1 Untreated wastewater (hereinafter referred to as raw water) A discharged from a meat center (slaughterhouse) located in Kumamoto Prefecture,
Treated water B in which the raw water was treated by a general activated sludge system installed in the company and currently in operation; and Treated water C in which the raw water was treated through the process according to the present invention shown in Figure 2. The results of the analysis at the Pharmaceutical Testing Center of the Kumamoto Prefectural Pharmacists Association were as shown in Table 1.

【table】

[Table] BOD is biochemical oxygen consumption, COD is chemical oxygen consumption, and SS is suspended solids. The analysis method is
From top to bottom, the above analysis items are Standard 12.1, Environment Agency Notification No. 59, Standard 17, Standard 21, and Ministry of Health, Labor and Welfare Construction Ordinance No. 1.
According to the attached table of Environment Agency Notification No. 64. The standard is
It is JISK0102. Experimental Example 2 Raw water A discharged from a meat processing plant (slaughterhouse) located in Kagoshima Prefecture and treated water C obtained by treating the raw water through the process according to the present invention shown in Fig. The results of the analysis by the Kagoshima Prefecture Pollution Control Association are as follows:
It was as shown in Table 2.

[Table] The analysis method was the same as in Experimental Example 1. Experimental Example 3 Raw water A discharged from a meat center (slaughterhouse) located in Kitakyushu City, and treated water B obtained by treating the raw water with a general activated sludge equipment installed at the company and currently in operation. The results of an analysis by the Kitakyushu City Environmental Improvement Association of the raw water and treated water C, which was processed through the process according to the present invention shown in Figure 2, are as follows.
The results were as shown in Table 3.

[Table] The analysis method was the same as in Experimental Example 1 except that SS was JISK0102-14-1. Experimental Example 4 Raw water A discharged from a meat processing plant (slaughterhouse) located in Fukuoka Prefecture and treated water C obtained by treating the raw water through the process according to the present invention shown in Fig. The results of the analysis conducted by the Japan Environmental Health Center were as shown in Table 4.

[Table] The analysis method was the same as in Experimental Example 1 except that the coliform count was determined using the MPN method. Experimental example 5 A certain chicken processing (broiler) located in Miyazaki prefecture
Raw water A discharged from the company, treated water B obtained by treating the raw water with a general activated sludge equipment installed in the company and currently in operation, and the raw water according to the present invention shown in FIG. The results of an analysis of the treated water C that was processed through the process by the Miyazaki Prefecture Pollution Control Association were as shown in Table 5.

【table】

[Table] The analysis method is the same as in Experimental Example 1 for the top five analysis items above. Items not yet listed are based on Appendix Table 7 of Environment Agency Notification No. 59. Experimental example 6 Conventionally, tap water was disinfected using sodium hypochlorite, and BOD and COD were treated using sulfuric acid.
SS treatment was performed using activated carbon. When the flocculant according to the present invention was added to this tap water intake (approximately 20 c.c. per 1 m ³ of water intake), the flocculation of organic matter was remarkable, and the numerical values for each inspection item were as follows: The reduction was several 10 to several 100 times lower than that of purified water, and the reduction in CCD was particularly remarkable. When the flocculant according to the present invention was added to conventional water purification, the flocculation of organic substances was clearly visible even when visually observed. In addition, in any of the above experimental examples, sample A
sample B had a weak rotten odor, while sample C had almost no odor. Moreover, Sample C was colorless and transparent. Sample C has been regenerated to the point where it can be used as a drink due to its high purifying power, and 20 people tasted it and all found that it tasted similar to so-called natural mineral water, which is lighter and sweeter than tap water. I got it. As is clear from the above, when the recycled water produced by the above device is used as factory water or water for various purposes other than washing water, it can be used as recycled water any number of times if the water after use is purified again by the above device. This can help conserve water resources. In addition, the aggregates separated by the above treatment are
Since it is an organic substance, it can be used as fertilizer or compost with appropriate treatment. (Effects of the Invention) As described above, according to the present invention, an animal bone-containing flocculant can be produced by a simple method by utilizing animal bones, which have conventionally been discarded without any use. According to this flocculant, after removing relatively large solids through primary filtration, a sufficient condensation reaction is carried out to purify wastewater, especially wastewater containing putrefactive organic matter such as animal origin. At the same time, it is possible to obtain reclaimed water that has been mineralized and purified to a drinkable level, which can be processed in a relatively short period of time.In addition, the equipment for this purpose has a relatively simple structure and is inexpensive, and requires less maintenance. It can be made easily. If the flocculant is made up of only animal bone solution, it is necessary to use a filter to separate the aggregates, but if the flocculant is made up of a mixture of iron, copper, etc. metal solution, , the aggregates coagulate and precipitate, making the separation process easier. Reclaimed water purified by the flocculant according to the present invention is suitable for reuse over a wide range of areas, and there is no risk of pollution even when it is discharged into natural water bodies. Furthermore, when the recycled water obtained according to the present invention is used, if the water after use is purified again according to the present invention, it can be used as recycled water any number of times, which is useful for saving water resources.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing an example of wastewater treatment using the flocculant according to the present invention, and FIG. 2 is a flowchart showing another example of the same wastewater treatment. 1,16...Animal bone-containing flocculant tank, 2,15...
...Neutralizer tank, 3, 12...Measuring tank, 4a, 13...
...Mixing tank, 4b, 14...Reaction tank, 5, 17...
Pressurized flotation tank, 6, 23, 25...filtration tank.

Claims (1)

[Scope of Claims] 1. An animal bone-containing flocculant comprising an osteolytic solution prepared by dissolving calcined powdered animal bone powder in sulfuric acid or hydrochloric acid. 2. An animal bone-containing flocculant obtained by uniformly mixing a bone dissolving solution obtained by dissolving calcined powdered animal bone powder in sulfuric acid or hydrochloric acid, and a metal dissolving solution obtained by dissolving iron or copper in sulfuric acid or hydrochloric acid. 3. Mix calcined and powdered animal bone powder with sulfuric acid or hydrochloric acid to obtain a bone solution, and on the other hand, mix iron or copper with sulfuric acid or hydrochloric acid to obtain a metal solution, and then mix both solutions. A method for producing an animal bone-containing flocculant, which comprises mixing and integrating. 4 Mix calcined and powdered animal bone powder with sulfuric acid or hydrochloric acid at a ratio of about 1 to 1.5 of the latter to about 1 kg of the former to dissolve the bone powder, then dilute with water and filter to obtain a bone dissolution solution, On the other hand, iron to copper and sulfuric acid to hydrochloric acid are mixed in a ratio of about 1 to 1.5 of the latter to about 100 g of the former, the iron to copper is dissolved, and then diluted with water and filtered to obtain a metal solution. The above-mentioned osteolytic solution and metal dissolving solution are mixed to about 1 for the former and about 1 for the latter.
A method for producing an animal bone-containing flocculant comprising a step of mixing and homogenizing at a volume ratio of 0.3 to 0.7. 5 An animal bone characterized in that an animal bone-containing flocculant consisting of a bone dissolving solution prepared by dissolving calcined and powdered animal bone powder in sulfuric acid or hydrochloric acid is used after adding an alkaline reactive material to the treatment solution. How to use the included flocculant. 6. An animal bone-containing flocculant made by uniformly mixing a bone dissolving solution obtained by dissolving calcined powdered animal bone powder in sulfuric acid or hydrochloric acid, and a metal dissolving solution obtained by dissolving iron or copper in sulfuric acid or hydrochloric acid. , A method for using an animal bone-containing flocculant, which comprises adding an alkaline reactive material to a treatment solution before use.