JP3345109B2 - Method for producing dry distilled condensed water-soluble liquid from soy sauce cake - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry distillation condensed water-soluble liquid obtained by carbonizing food such as cereals, beans and dried meat or / and food lees such as soy sauce lees, beer lees, sake lees and oil lees. Vinegar liquid), oily liquid, charcoal, and non-condensable gas.

[0002]

2. Description of the Related Art Conventionally, a method of carbonizing wood to produce charcoal, wood vinegar liquid, oily components, and the like has long been used as charcoal grilling. In addition, a simple charcoal burning method using a drum, an oil can, a block, or the like is known. In addition, as a method of industrially producing coal, a fluidized bed method, a trolley method, a method using a rotary kiln furnace, a method using a vertical continuous carbonization furnace, a screw method, and the like, for example, in the fluidized bed method, The wood chips used as raw materials are stirred and mixed by blowing in air through a blower.In the screw method, wood flour is used as the raw material, and the wood flour is carbonized while being carried by the screw in the carbonization furnace. I have.

[0003] These conventional carbonization methods are originally a method and an apparatus for producing charcoal, and are not used for producing a carbonized condensed aqueous solution or an oily liquid. A method and an apparatus mainly for producing a condensed aqueous solution or an oily liquid have not been established. further,
Foods such as rice, wheat, soybeans, soybeans, red beans, coffee beans, dried bonito, dried meat, and food lees such as soy sauce lees, beer lees, and okara are carbonized to produce useful components such as water-soluble liquids, oily liquids, and charcoal. As a method, after filling these raw materials in a carbonization furnace, other than a laboratory method of performing carbonization by heating as it is sealed,
There is no industrially known method for efficiently producing useful components such as a dry distillation condensed aqueous solution and an oily solution.

Conventionally, wood vinegar has been produced from trees such as hardwoods and conifers, and it is known that a liquid similar to wood vinegar can be collected from herbaceous plants other than trees. However, none of them can be expected to be effective as wood vinegar liquid [“Agricultural chemicals reduced with wood vinegar and charcoal-How to use and how to make-”, published by The Agricultural and Mountain Fishing Village Cultural Association
(January 20, 1992)), it was completely unthinkable to produce a vinegar solution having marketability from brewed lees and bean lees.

[0005]

Until now, the processing of food lees discharged from manufacturing processes in the food industry, such as soy sauce lees, beer lees, and okara, has been mainly incinerated and dumped.
At present, it has not been actively recycled. Therefore, establishment of a method for recycling these food wastes discharged in large quantities has long been desired. In recent years, due to soaring processing costs and legal regulations on disposal,
It is becoming increasingly difficult to dispose of them easily.

The present invention has been made in view of the above-mentioned points, and an object of the present invention is to efficiently produce dry-condensed water-soluble liquid, oil-based liquid and charcoal, which are valuable substances, by carbonizing these food lees. It is to provide a method. Also, cereals,
Techniques for producing carbonized condensed water-soluble liquids by carbonizing foods such as beans and dried meats have not been known so far. Therefore, another object of the present invention is to efficiently convert aqueous liquids from these raw materials. It is to provide a manufacturing method.

[0007]

To achieve SUMMARY and effects of the Invention The above object, a method of manufacturing a dry distillation condensate aqueous solution from the soy sauce cake of the present invention (vinegar) is-heated sauce cake as a raw material
This is a method of carbonizing to obtain gas and charcoal, cooling the gas and condensing the condensable gas in the gas to form a carbonized condensed water-soluble liquid and oily liquid. The temperature of the raw material in the dry distillation furnace at the time of dry distillation is controlled in the range of 250 to 550 ° C. where the yield of the dry distilled condensed water-soluble liquid (vinegar liquid) and the oily liquid is increased, and the oil obtained by dry distillation is obtained. It is characterized in that liquid and non-condensable gas are burned and used as a heat source for carbonization. Table 1 shows the vinegar distillate amount and the pH of the vinegar solution when the soy sauce cake was carbonized without stirring and when the same soy sauce cake was carbonized by stirring (10 rpm). From Table 1, it can be seen that the vinegar distillate amount was significantly increased by stirring, and the pH of the vinegar was closer to neutral by stirring. This indicates that stirring at the time of carbonization is extremely effective.

[0008]

[Table 1]

In the above method, it is desirable to carry out carbonization while controlling the cooling temperature of the generated gas at a temperature higher than the solidification temperature of the oily liquid obtained after the condensation and lower than the condensation temperature. In addition, the temperature of the raw material in the
You control the range of 250 ~ 550 ℃. In this case, when the temperature of the raw material is lower than 250 ° C., the yield of the vinegar solution is low,
And originally reduced the amount of active ingredient contained in vinegar solution, moreover, there is a disadvantage that pH is increased to 7.0 or higher, while if it exceeds 550 ° C., the yield of vinegar to the heating volume And the pH of the vinegar solution exceeds 7.0, and furthermore, there is a disadvantage that an expensive furnace material is required for performing this operation.

Moreover, it uses the dry distillation of the heat source by burning the oily liquid及beauty noncondensable gas obtained by dry distillation. Further, it is desirable to control the pH of the dry distillation condensed aqueous solution by adjusting the carbon / nitrogen ratio (C / N ratio) of the raw material components.
In this case, the C / N ratio is, for example, 12.0 to
12.5 is preferable, and the pH is 6.0 to 8.0.
0, preferably 6.5 to 7.0.

[0011] Further, by blowing air or oxygen into the carbonization furnace while adjusting the carbonization during the carbonization, the water-soluble liquid of the carbonization condensed water is removed.
It is desirable to control the pH and change the scent of the dry distilled condensed aqueous solution. In this case, it is preferable that the amount of air blown be, for example, 1000 m ³ air / hr and the raw material t of soy sauce cake. In addition, it is desirable to add water to the charcoal obtained by dry distillation to desalinate.

In the present invention, as described above, in the step of dry-distilling soy sauce cake to produce a dry-distilled condensed water-soluble liquid, an oily liquid, and charcoal, the raw materials are heated while being stirred and mixed during the dry distillation. Further, controlling the cooling temperature of the generated gas between the freezing point and the condensing point of the oily liquid, controlling the dry distillation temperature to a constant value between 250 and 550 ° C., and controlling the heat required for dry distillation. It is characterized by supplementing it by burning oily liquid and non-condensable gas obtained by carbonizing energy.

Hereinafter, the method of the present invention will be described with reference to FIG. After the raw materials are put into the dry distillation furnace 10 and the lid 12 is closed and sealed, heating of the furnace is started by a heater 14 such as a mantle heater, and the whole furnace is heated at a predetermined temperature. Raw materials used at this time include foods such as rice, wheat, soybeans, red beans, coffee beans, bonito, dried meat, and / or food lees such as soy sauce lees, beer lees, sake lees, and juice lees. In addition, raw materials obtained by mixing these foods and / or food lees can also be used. After charging the raw materials and switching on the heating element, the stirrer is started. The stirring speed at this time may be any speed as long as the raw materials can be uniformly mixed.
rpm or less is preferred.

The heating temperature is detected by a temperature measuring element (temperature sensor) T3 arranged on the side of the dry distillation furnace 10, and this signal is inputted to a control device (not shown) of the heater 14 so that the heating temperature becomes a predetermined heating temperature. The distillation is performed while controlling the temperature. More accurate and reliable temperature control is possible by installing the temperature measuring element T3 in the center of the stirred material and in the head space inside the furnace so that overheating or insufficient heating does not occur. Becomes The temperature of carbonization, as described above, dry distillate condensed aqueous liquid yield of (vinegar) and oily liquid rises 250
Select temperature range to 550 ° C., that control constant. At this time, in order to obtain the thermal energy necessary for dry distillation, the oily liquid product, Ru by burning non-condensable gases.

Next, the dry distillation gas distilled out by heating is cooled using the indirect cooler 16 and captured as a condensate.
Recovers water-soluble and oil-based liquids. At this time, the temperature for cooling may be not less than the coagulation temperature of the oily liquid thus obtained and not more than the condensation temperature. In particular,
In the range of 30 to 60 ° C., the viscosity of the condensed liquid is low, and the yield of the dry-distilled condensed water-soluble liquid and oily liquid is high. Next, the heating method of the carbonization furnace 10 is preferably to quickly raise the carbonization temperature to a predetermined carbonization temperature. be able to. The time for maintaining the dry distillation temperature after reaching the predetermined temperature may be determined in consideration of the state of distillation of the dry distillation condensed aqueous solution and the oily liquid, and is not particularly limited. Usually, the point at which the distillation of the carbonized condensed aqueous solution and the oily liquid is completed is regarded as the end of the carbonization operation. However, if the desired amount can be secured, the carbonization may be stopped halfway. 18 is a stirring motor, 20 is a stirrer, 22 is a heater, 24 is an air supply pipe, 26 is a raw material such as soy sauce cake, 28
Denotes a receiving container, 30 denotes a dry distillation condensed aqueous solution (vinegar solution), 32 denotes an oily liquid, and T1, T2, and T4 denote temperature sensors (temperature sensors). In addition, insert the tip of the air supply pipe into the raw material,
It may be located at the bottom of the raw material. Further, an oxygen supply pipe may be provided instead of the air supply pipe.

FIG. 2 shows a flow around the carbonization furnace 10. The vinegar liquid (crude vinegar liquid) 30 distilled out in the receiving container 28 in FIG. 1 is further purified to separate tar (oil component), and as a purified vinegar liquid as an agricultural material such as a plant growth promoter. Used. The tar (oil component) and the non-condensable gas are used as fuel. Moreover, charcoal which is a carbonization residue is used as fuel or agricultural material after desalination. In this case, by adding water to the charcoal, the salt in the charcoal is easily dissolved in the water, and the solid-liquid separation after the dissolution is very easy, so that the desalting treatment can be easily performed.

The soy sauce cake contains about 3% by weight of tyrosine, which is a kind of amino acid. As shown in FIG. 3, the present inventors added tyrosine to the soy sauce cake to increase the nitrogen content. By doing so, it was found that the pH value of the obtained vinegar solution was increased. From these facts, by adjusting the C / N ratio of the raw material components, it becomes possible to control the pH of the vinegar to around neutral suitable for use as agricultural materials.

FIG. 4 shows the relationship between the amount of air blown and the pH of the vinegar solution. FIG. 4 shows that the pH of the vinegar solution can be controlled to around neutral by blowing air into the raw material in the carbonization furnace. In addition, the scent of the vinegar obtained by dry-distilling while blowing air in this way had less odor and was improved than the scent of the vinegar obtained without blowing air at all.

FIG. 5 shows the changes over time in the amount of vinegar, the amount of oily liquid and the temperature during dry distillation. FIG. 5 shows that when the soy sauce cake temperature T1 was dry-distilled at about 290 ° C., about 30 ml of vinegar was distilled out.

FIG. 6 shows the effects of the carbonization temperature on the amount of vinegar, the amount of oily solution, and the pH of the vinegar. In FIG. 6, the vinegar distillate amount and the oily liquid distillate amount increase as the carbonization temperature increases, but the pH value of the vinegar solution exhibits acidity around pH 5.6 when the carbonization temperature is around 250 ° C., It approaches pH 7 as the temperature increases from 250 ° C. This indicates that the carbonization temperature is preferably set to 250 ° C. or higher.

FIG. 7 shows the influence of the raw material moisture on the vinegar solution amount, the oily solution amount and the pH of the vinegar solution. From FIG. 7, as the water content increases, the apparent amount of vinegar produced increases,
It can be seen that the corrected vinegar amount obtained by subtracting the water amount from this amount is substantially constant, and that the pH value does not fluctuate significantly. This indicates that the raw material water content does not significantly affect the vinegar liquid distillate amount, the oily liquid distillate amount, and the pH of the vinegar liquid.

[0022]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples, and may be carried out by appropriately changing the scope of the invention without changing its gist. Is possible. Example 1 The apparatus shown in FIG. 1 was used as a carbonization test apparatus in this example. First, 100 g of soy sauce cake having the properties shown in Table 2 was collected, put into a carbonization furnace 10, covered with the furnace top lid 12, and the rubbed portions were tightened and clamped at three places with clamps. Next, nitrogen gas was supplied at a flow rate of 1 liter / min.
After flowing into the furnace for 0 minute and replacing the air remaining in the furnace with nitrogen gas, tap water was started to flow into the cooling pipe of the cooler 16, and the upper lid portion was heated by the ribbon heater 22.

[0023]

[Table 2]

When the temperature of the entire top lid reached 150 ° C., the stirrer 20 was started at a rotation speed of 10 rpm, and at the same time, the heating of the furnace was started by turning on the mantle heater 14 for heating the carbonization furnace. Heating is controlled by detecting the temperature with a thermocouple type temperature sensor T3 installed between the mantle heater and the furnace, and feeding back the signal to a control device installed on the mantle heater to set a preset 350 ° C.
℃ controlled.

The temperature of the soy sauce cake in the furnace is set to about 30 after the start of heating.
It reached 350 ° C. in minutes. Distillation of the dry-distilled condensed water-soluble liquid (vinegar liquid) started 10 minutes after the start of heating, and was stopped 60 minutes later. On the other hand, the distillation of the oily liquid started 20 minutes after heating, and the distillation was completed 60 minutes after the heating as in the case of the water-soluble liquid.
The amounts of the water-soluble liquid and the oil-based liquid thus obtained, and the analysis values of the obtained water-soluble liquid were as follows. Vinegar volume: 31 ml Oil volume: 17 ml pH: 6.9 Brix: 20.3 (refractive index)

After the furnace was sufficiently cooled, the charcoal remaining in the furnace was observed. As a result, charcoal having uniform physical properties was obtained. Since the weight of this charcoal was 30 g, it was considered that about 20 g of gas could not be collected by this test apparatus. The analysis values of the oily liquid thus obtained are shown in Table 3.
Shown in This oily liquid has a calorific value of 8000-9000ca
l / g, and it was found that when fueled in the air, it was slightly inferior to commercial heavy oil and commercial light oil, but generated enough heat as fuel. In the case of industrial use, it is necessary that the fluidity is high, but the viscosity at each temperature is small (light) as compared with commercial heavy oil. From these facts, it can be understood that the present oily liquid can be used as a heat source necessary for dry distillation.

[0027]

[Table 3]

Comparative Example 1 After 100 g of dried soy sauce cake (water content: 10%) was put into a 1-liter stainless steel pot, tap water was started to flow into the cooling pipe of the cooler, and then the container was discharged to the gas cooling pipe. Only the container was sealed, and the bottom of the container was directly heated with a gas fire. Heating was continued for about 60 minutes after gas generation, and after confirming that almost no condensate had come out, the gas fire was extinguished and dry distillation was completed. 21 ml of dry distilled condensed aqueous solution and 10 ml of oily solution could be obtained. The pH of the aqueous solution obtained at this time was 8.6,
Brix was: 17.0.

[0029]

As described above, the present invention has the following effects. (1) The raw materials are uniformly mixed by stirring and mixing when the raw materials are dry-distilled, so that a dry-distilled condensed water-soluble liquid (vinegar liquid) having a constant quality can be produced more quickly. (2) The temperature of the raw material in the carbonization furnace at the time of carbonization is 250
By controlling the temperature within the range of ~ 550 ° C,
Liquids (vinegar) and oily liquids have higher yields. (3) Combustion of oily liquid and non-condensable gas
It can be baked and used as a heat source for carbonization. ( 4 ) When adjusting the C / N (carbon / nitrogen) ratio of the components of the raw material, the pH of the vinegar solution can be controlled to around neutral. ( 5 ) When a small amount of air or oxygen is blown during heating, it is possible to control the pH of the vinegar to near neutrality and improve the fragrance.

[Brief description of the drawings]

FIG. 1: Soy sauce cake of the present invention is distilled water condensed water-soluble liquid (vinegar liquid)
FIG. 1 is a schematic configuration diagram illustrating an example of an apparatus for performing a method for manufacturing a carbon dioxide, and illustrating a carbonization test apparatus used in Examples.

FIG. 2 is a flow sheet showing an example around the apparatus shown in FIG.

FIG. 3 is a graph showing the relationship between the content of tyrosine in soy sauce cake and the pH of vinegar.

FIG. 4 is a graph showing the relationship between the amount of air blown and the pH of the vinegar solution.

FIG. 5 is a graph showing the relationship between the amount of vinegar, the amount of oily liquid, the temperature and the carbonization time.

FIG. 6 is a graph showing the relationship between the vinegar solution amount, the oily solution amount, the pH of the vinegar solution, and the carbonization temperature.

FIG. 7 is a graph showing the relationship between the amount of vinegar solution, the amount of oily solution, the pH of vinegar solution, and the raw material moisture.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Dry distillation furnace 14 Heater 16 Cooler 20 Stirrer 24 Air supply pipe 26 Raw material 28 Receiving container 30 Dry distillation condensed water-soluble liquid (vinegar liquid) 32 Oily liquid

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hayami Ito 1-1, Kawasaki-cho, Akashi-shi, Hyogo Kawasaki Heavy Industries, Ltd. Inside the Akashi Plant (72) Inventor Daisaku Sasaki 3-1-1, Higashi-Kawasaki-cho, Chuo-ku, Kobe-shi 1 Kobe Plant, Kawasaki Heavy Industries, Ltd. (72) Katsumi Yuasa, Inventor 399 Noda, Noda, Chiba Prefecture Kikkoman Corporation (72) Inventor Norikazu Fujii 399, Noda, Noda City, Chiba Prefecture Kikkoman Corporation (72 ) Inventor Makoto Okayasu 399 Noda, Noda City, Chiba Pref. Kikkoman Corporation (56) References JP-A-57-145177 (JP, A) JP-A-50-160302 (JP, A) JP-A 49-9069 (JP, a) JP flat 4-351693 (JP, a) JP flat 2-247284 (JP, a) JP flat 1-168796 (JP, a) (58 ) investigated the field (Int.Cl. ⁷ DB name) C10B 53/02 A23L 1/23 C10G 1/00

Claims (5)

(57) [Claims] 1. A method of heating and dry-distilling soy sauce cake as a raw material to obtain gas and charcoal, cooling the gas and condensing a condensable gas in the gas to form a dry-distilled condensed aqueous solution and an oily liquid. The raw material is dry-distilled while being stirred and mixed during heating, and the temperature of the raw material in the dry-distillation furnace at the time of dry distillation is controlled in the range of 250 to 550 ° C. where the yield of the dry-distilled condensed water-soluble liquid and oily liquid is increased. A method for producing a dry-distilled condensed water-soluble liquid from soy sauce cake, wherein an oily liquid and a non-condensable gas obtained by dry-distillation are burned and used as a heat source for dry-distillation. 2. The dry distillation while controlling the cooling temperature of the generated gas to be in the range of not less than the solidification temperature of the oily liquid obtained after condensation and not more than the condensation temperature.
A method for producing a dry-distilled condensed aqueous solution from the soy sauce cake described in the above. 3. The dry-distilled condensed aqueous solution is produced from soy sauce cake according to claim 1, wherein the pH of the dry-distilled condensed aqueous solution is controlled by adjusting the carbon / nitrogen ratio of the raw material components. how to. 4. A method of controlling the pH of the dry-distilled condensed water-soluble liquid and changing the scent of the dry-distilled condensed water-soluble liquid by blowing air or oxygen into the dry-distilling furnace while adjusting the pressure during the dry distillation. A method for producing a dry-distilled condensed aqueous solution from soy sauce cake according to claim 1, 2 or 3. 5. A sauce according to claim 1, 2, 3 or 4, wherein the desalting by adding water to the resulting coal by dry distillation
Method for producing a dry distillation condensate aqueous solution from the oil dregs.