JP4140717B2 - Method for producing liquid antifreeze - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention is for melting snow in cold districts and the like and preventing freezing of snow and ice.LiquidIn particular, calcium acetate is included as a liquid cryoprotectant.LiquidThe present invention relates to a method for producing a frozen antifreeze.
[0002]
[Prior art]
Conventionally, various substances have been used as antifreeze agents. Among them, chloride is accompanied by a salt damage problem, and instead of this, acetate type antifreeze agents have been used. Yes. Known acetate-based antifreezing agents include, for example, potassium acetate, sodium acetate, calcium acetate and the like formed in a granular form. For example, see Patent Document 1 (Japanese Patent Laid-Open No. 62-576).
[0003]
Such anti-freezing agents are used, for example, by spraying on highways, etc. However, when granular, they are slow-acting and sometimes difficult to spray. To make an aqueous solution and spraying this aqueous solution. This facilitates spraying and achieves immediate effect. A technique for spraying an antifreezing agent in an aqueous solution is a magnesium oxide salt, but is described, for example, in Patent Document 2 (Japanese Patent Laid-Open No. 10-298540).
[0004]
[Patent Document 1]
JP-A 62-576
[Patent Document 2]
Japanese Patent Laid-Open No. 10-298540
[0005]
[Problems to be solved by the invention]
By the way, in order to form the antifreeze agent in a granular form, it is necessary to separately provide equipment required for the granular form such as heating to evaporate water, and the man-hour is increased accordingly, which increases the cost. There was a problem. Furthermore, if this is made liquid, the operation | work for making it liquid will be needed, and also in this respect, cost will increase further.
[0006]
For this reason, it is conceivable that the liquid is formed from the beginning without being granulated. However, even if it is made liquid, the problem of precipitation occurs when the concentration is too high, and the ice melting effect is inferior when the concentration is low. , Storage costs will be high. In particular, calcium acetate is extremely difficult to produce in a liquid state because of its property of decreasing solubility as the temperature increases.
[0007]
  The present invention has been made in view of the above-mentioned problems, and in the case of having calcium acetate, it can be produced with as high a dissolution rate as possible, can be produced at low cost, and can be easily sprayed to achieve immediate effect. To be able toLiquidAn object of the present invention is to provide a method for producing a frozen antifreeze.
[0008]
[Means for Solving the Problems]
  Manufactured by the method for producing a liquid antifreeze of the present inventionLiquid antifreeze is a liquid antifreeze containing calcium acetate,
13.7 to 14.2% by mass of calcium acetate,
27.0 to 28.8% by mass of potassium acetate,
50.0 to 52.3% by mass of water,
It has the configuration that it has.
[0009]
This liquid antifreeze is mixed with potassium acetate in a state where calcium acetate keeps its dissolution rate high. With calcium acetate alone, the melting concentration is about 30% by mass, so that the ice melting effect is limited. However, since potassium acetate is added, the ice melting effect is improved. Thereby, spreading becomes easy and the immediate effect of melting ice is achieved. Potassium acetate is expensive, but in the present invention, potassium acetate is added in a state that keeps the liquid state to a minimum, and an anti-freezing agent having a higher melting effect than calcium acetate is as inexpensive as possible. Can be manufactured.
[0010]
In this case, it is effective to have a configuration containing 4.7 to 9.3 mass% of glycerin. By adding glycerin, moderate viscosity is imparted and the antifreezing effect is enhanced.
[0011]
Moreover, the method for producing a liquid antifreeze of the present invention for solving the above-described problem has an acetic acid mixing step of mixing calcium carbonate and / or calcium oxide and acetic acid, and the acetic acid in the acetic acid mixing step is mixed. In the method for producing a liquid cryoprotectant for producing a liquid cryoprotectant containing calcium acetate by mixing,
In the acetic acid mixing step, 750 ml of acetic acid having a concentration of 18 to 40% by mass is mixed with 100 g of calcium carbonate and / or calcium oxide so that the amount of calcium acetate is 30% by mass or less.
[0012]
Here, the relationship between calcium carbonate and / or calcium oxide and the amount and concentration of acetic acid will be described. The concentration is 18 to 40% by mass with respect to 100 g of calcium carbonate and / or calcium oxide (amount of scallops in Examples). When 750 ml of acetic acid is mixed, the amount of calcium acetate after the reaction becomes 30% by mass or less. For this reason, liquid calcium acetate is the limit at which a solubility of 30% by mass or less is not practically precipitated from conditions such as outside air temperature or room temperature, so that precipitation is prevented and the dissolution rate is increased as much as possible. it can.
[0013]
It is also possible to prepare calcium acetate powder by reacting calcium carbonate and / or calcium oxide with acetic acid at an appropriate concentration, and then measuring calcium acetate and diluting to 30% by mass with water. It is. However, the method requires a manufacturing process for obtaining powder, and the efficiency is low and the cost is high. However, in the present invention, the reaction process and the liquid adjustment process are performed once from the viewpoint of production efficiency (economical). Therefore, it is efficient and can significantly reduce the cost.
[0014]
Furthermore, the reaction step is performed in an acetic acid excess region. Originally, the chemical reaction is carried out at an optimal molar ratio, but in this case, calcium carbonate and / or calcium oxide reacts with acetic acid to form calcium acetate, but as the reaction time proceeds, the calcium carbonate also decreases and acetic acid The concentration also decreases, the reaction contact ratio between the two decreases, and the reaction time for producing calcium acetate is extremely delayed. In the present invention, the reaction is carried out in an acetic acid excess region so that calcium carbonate can be consumed quickly, and calcium acetate can be generated in a short time. This also improves the production efficiency.
[0015]
However, since the use of acetic acid in an excessive amount is meaningless in terms of production efficiency, the present invention defines the appropriate amount.
That is, desirably, the concentration of the acetic acid to be mixed is 20 to 30% by mass. More preferably, the concentration of the acetic acid to be mixed is 27 ± 1% by mass.
[0016]
In the present invention, if necessary, an adjustment step of adjusting the solution produced in the acetic acid mixing step is provided, and in the adjustment step, equimolar amount of potassium hydroxide per 1 mol of unreacted acetic acid in the solution. As described above, the solution is added so that the pH of the solution after the addition is in the range of 6.5 to 9.0.
[0017]
Thereby, potassium acetate is produced and mixed with calcium acetate to form a liquid. In this case, it is effective to add potassium acetate in a solubility limit amount.
With calcium acetate alone, the melting concentration is about 30% by mass, so there is a limit to the ice melting effect. However, by mixing potassium acetate, the ice melting effect can be improved. However, potassium acetate is expensive, but in the present invention, potassium acetate is added in a state that keeps the liquid state to a minimum, and thus an antifreezing agent having a higher melting effect than calcium acetate is possible. It can be manufactured as cheaply as possible.
[0018]
Moreover, in this invention, since the production | generation reaction process of calcium acetate is performed in an acetic acid excess area | region, although an acetic acid smell is added, potassium hydroxide is added and pH of a solution is 6.5-9.0. Since the amount is within the range, excess acetic acid reacts with potassium hydroxide to produce potassium acetate and remove the acetic acid odor. That is, surplus acetic acid is removed by producing potassium acetate and adjusting the pH, and a deodorizing effect is achieved.
[0019]
Furthermore, alkalinity is imparted by adding potassium hydroxide and adjusting the pH, and the rust prevention effect is enhanced. Although excessive potassium hydroxide alone may promote rust, the present invention has specified an appropriate concentration.
[0020]
A more specific adjustment step is performed by adding water, acetic acid, and potassium hydroxide. These liquids are mixed in advance and added to the solution produced in the acetic acid mixing step.
[0021]
And it is effective to add water, acetic acid, and potassium hydroxide by the calculation formula of the production amount (B) of the antifreezing agent listed below.
B = A + X (KOH) + Y (water) + Z (CH_ThreeCOOH)
here
B: Production amount (mass) of antifreezing agent
A: Amount (mass) of the solution produced in the acetic acid mixing step
X: KOH amount (mass) of (0.20 to 0.35) times the mass of A solution
Y: Amount of water (mass) that is (0.50 to 0.80) times the mass of solution A
Z: The amount (mass) of acetic acid (0.10 to 0.20) times the mass of the solution A.
Preferably
X: KOH amount (mass) of (0.23 to 0.30) times the mass of A solution
Y: Amount of water (mass) that is (0.51 to 0.70) times the mass of solution A
Z: It is the amount (mass) of acetic acid (0.13-0.17) times the mass of A solution.
Most preferably
X: KOH amount (mass) of (0.25 to 0.28) times the mass of the A solution
Y: Amount of water (mass) that is (0.585 to 0.65) times the mass of solution A
Z: The amount (mass) of acetic acid (0.15 to 0.16) times the mass of the A solution.
[0022]
When the amount of water is small, calcium acetate precipitates, while when the amount of water is large, the ice melting effect is reduced. The above range is an appropriate addition amount. Outside this range, it becomes difficult to maintain the liquid state. When water, acetic acid and potassium hydroxide are added, potassium acetate is produced while maintaining the solution state by the reaction of acetic acid, potassium hydroxide and water. As a result, surplus acetic acid reacts with potassium hydroxide to remove the acetic acid odor, and the production of potassium acetate produces an antifreezing agent having a high melting effect.
In addition, although only a potassium acetate can be added and the ice melting effect can be improved, the acetic acid odor cannot be removed.
[0023]
In this case, it is effective to add glycerin. By adding glycerin, moderate viscosity is imparted and the antifreezing effect is enhanced.
[0024]
And in this invention, it is set as the structure which provides a fragrance as needed. The imparting of fragrance is performed by at least one of a method of separately adding a fragrance or a method of using an aromatic material. Acetic acid odor is removed.
[0025]
In this case, an acetic acid production process for producing the acetic acid to be used as a raw material waste is provided, and in this acetic acid production process, apple squeezes are used as the fruit and vegetable waste, and the aroma of apple is given to the acetic acid produced. It is effective. Since the fragrance is originally added to the raw material acetic acid, it is more efficient than the case where a separate fragrance is added. Therefore, it becomes possible to produce an antifreezing agent using the waste of fruits and vegetables as a raw material, and the waste can be effectively used.
[0026]
Further, in the present invention, if necessary, a calcium production process for producing calcium carbonate and / or calcium oxide to be used as a raw material is provided, and in the calcium production process, the shell is washed, and the washed shell The pulverized powder is fired to produce calcium carbonate and / or calcium oxide. Therefore, it becomes possible to produce an antifreezing agent using shellfish waste as a raw material, and the waste can be effectively used.
[0027]
In this case, it is effective to set the firing temperature of the granular material to 500 ° C. or higher. Although it reacts with acetic acid at 500 ° C. or lower, the reaction time becomes longer and the production efficiency of calcium acetate becomes worse. The reactivity with acetic acid becomes good at 500 ° C. or higher. Desirably, it is effective to set the firing temperature of the granular material to 600 ° C to 800 ° C. When the temperature exceeds 800 ° C., the reactivity is improved, but the energy consumption is increased, so that the cost is increased. More preferably, it is effective to set the firing temperature of the above-mentioned granular material to 650 ° C. ± 20 ° C. Since it can maintain satisfactory reactivity and does not become expensive, it is economical.
[0028]
And if needed, it is set as the structure which used the shell of the scallop as a shell. These wastes can be used effectively.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.A method for producing such a liquid antifreezing agent will be described.
[0030]
The method for producing a liquid antifreeze according to the embodiment is a method for producing a liquid antifreeze containing calcium acetate as shown in FIG. 1, for example, as shown in FIG. Realized by the manufacturing system. The basic configuration of this system is a calcium production apparatus 1 that produces calcium carbonate and / or calcium oxide using shells as a raw material, an acetic acid production apparatus 10 that produces acetic acid from wastes of fruits and vegetables, and a calcium production apparatus 1. A calcium acetate production device 40 for producing calcium acetate in liquid form by mixing the produced calcium carbonate and / or calcium oxide and acetic acid produced by the acetic acid production device 10, and a solution generated by the calcium acetate production device 40. And an adjusting device 60 for adjusting.
[0031]
This manufacturing system uses apple pomace as a waste product. Apple pomace is a squeezed residue produced from commercially available apple juice, and is obtained from an apple juice manufacturing plant or the like. In the present invention, the present invention is not limited to apple pomace.
In addition, scallop shells as waste are used as shells. A shell obtained by collecting scallops from natural or cultured scallops and obtained from a scallop processing plant. The present invention is not limited to scallops.
[0032]
As shown in FIG. 2 and FIG. 3, the calcium production apparatus 1 is transported by a cleaning machine 3 for cleaning the shells transported by the transporting machine 2 with tap water, and from the cleaning machine 3 via the conveyor 4. A pulverizer 5 for pulverizing the washed shells that have been charged to form calcium carbonate particles, and a pulverized calcium carbonate powder that is conveyed from the pulverizer 5 through a conveyor 6 and calcined. And a firing machine 7 for making calcium and / or calcium oxide powder. In FIG. 3, reference numerals 8 a and 8 b denote a cyclone and an exhaust fan that process the gas from the calciner 7, and 9 denotes a transporter that transports calcium carbonate and / or calcium oxide powder to the calcium acetate production apparatus 40.
[0033]
As shown in FIGS. 2, 4, and 5, the acetic acid production apparatus 10 includes an ethanol generation unit 11 that generates ethanol from squeezed straw of apples as waste of fruits and vegetables, and ethanol generated by the ethanol generation unit 11. And an acetic acid generator 20 for generating acetic acid.
[0034]
The ethanol production unit 11 includes an ethanol fermenter 12 that inoculates a raw material with an enzyme, water, and a mutant of Candida Shehatae, and ferments the raw material while stirring the raw material at a predetermined temperature. In FIG. 4, the code | symbol 13 is a hopper which supplies the pomace of an apple, 14 is the stirrer which stirs the raw material of the ethanol fermentation tank 12, 15 is heated and cooled to the predetermined temperature by heating and cooling the ethanol fermentation tank 12 with steam and cooling water. A temperature controller 16 is a pump that feeds the fermented raw material to the acetic acid generator 20.
[0035]
The acetic acid production | generation part 20 is equipped with the acetic acid fermenter 21 which ferments a raw material, inoculating acetic acid bacteria to a raw material, stirring at predetermined temperature, and aeration, as shown in FIG.2 and FIG.4. In FIG. 4, the code | symbol 22 is an air supply machine which supplies aseptic air to the acetic acid fermentation tank 21, 23 is a stirrer which stirs the raw material of the acetic acid fermentation tank 21, 24 is the temperature which adjusts the temperature in the acetic acid fermentation tank 21 with cooling water. A regulator 25 is a gas vent machine that exhausts unnecessary gas, and 26 is a pump that feeds the fermented raw material to a centrifuge 30 described later.
In this acetic acid fermenter 21, for example, an inoculum of acetic acid bacteria for acetic acid fermentation is 1 × 10⁶ Inoculate to adjust to / ml, inoculate constantly, and perform fermentation at a temperature of 25 ° C. for 14 days.
[0036]
Moreover, the acetic acid production | generation part 20 is isolate | separated with the centrifuge 30 which centrifuges the raw material which finished fermentation in the acetic acid fermenter 21 and extracts acetic acid, and the centrifuge 30, as shown in FIG.2 and FIG.5. And acetic acid storage tank 31 for storing acetic acid. In the acetic acid storage tank 31, glacial acetic acid is appropriately added to adjust the acetic acid concentration to, for example, about 27 ± 1% by mass.
In FIG. 5, reference numeral 32 is a stirrer that stirs the raw material of the acetic acid storage tank 31, 33 is a temperature controller that adjusts the temperature in the acetic acid storage tank 31 with cooling water, and 34 supplies acetic acid to the calcium acetate production apparatus 40. A pump 35 is a regulator that adjusts the amount of acetic acid supplied by bypassing the acetic acid from the pump 34 to the acetic acid reservoir 31.
[0037]
As shown in FIGS. 2 and 6, the calcium acetate production apparatus 40 includes a mixing mixer 41 that injects acetic acid into the supplied calcium carbonate and / or calcium oxide and stirs while adjusting the temperature. In FIG. 6, reference numeral 42 denotes a hopper that supplies calcium carbonate and / or calcium oxide into the mixing mixer 41, and 44 and 45 denote a cyclone and an exhaust fan that process gas from the mixing mixer 41.
[0038]
Moreover, in the manufacturing method of the liquid antifreezing agent which concerns on this Embodiment, as shown in FIG.2 and FIG.7, the feed manufacturing apparatus 50 which manufactures a feed from the residue produced when manufacturing an acetic acid with the acetic acid manufacturing apparatus 10 includes. Is provided. As shown in FIG. 7, the feed production apparatus 50 includes a dryer 51 that dries the remaining residue from which acetic acid has been separated by the centrifuge 30. In FIG. 7, reference numeral 52 denotes a conveyor that conveys the residue and puts it into the dryer 51, 53 is a burner device that supplies a heat source to the dryer 51, and 54 discharges and conveys the dried residue from the dryer 51 as feed. Conveyors 55 and 56 are a cyclone and an exhaust fan for processing gas from feed on the conveyor 54.
[0039]
Further, as shown in FIGS. 2 and 8, the adjusting device 60 includes a mixing mixer 61 that adds water, acetic acid, and potassium hydroxide to the solution produced by the calcium acetate production device 40 and stirs while adjusting the temperature. It is prepared for.
[0040]
Therefore, according to the method for manufacturing a liquid antifreeze according to this embodiment, the liquid antifreeze is manufactured according to the steps shown in FIG.
[0041]
(1) Calcium production process
First, in the calcium production apparatus 1, as shown in FIGS. 2 and 3, when the shell is transported by the transporter 2 and is put into the washing machine 3, the introduced shell is washed with tap water by the cleaning machine 3. The Thereafter, the washed shells are transferred to the pulverizer 5 via the conveyor 4 and charged, and the shells cleaned by the pulverizer 5 are pulverized to form calcium carbonate particles.
Then, the calcium carbonate powder is conveyed from the pulverizer 5 via the conveyor 4, put into the baking machine 7 and baked. Here, the firing temperature of the granular material is set to 500 ° C. or higher, desirably 600 ° C. to 800 ° C., and more desirably 650 ° C. ± 20 ° C.
As a result, calcium carbonate and / or calcium oxide particles are formed. The calcium carbonate and / or calcium oxide powder is conveyed to the hopper 42 of the calcium acetate production apparatus 40 by the conveyor 9.
[0042]
(2) Acetic acid production process
On the other hand, in the acetic acid production apparatus 10, as shown in FIG.2 and FIG.4, in the ethanol production | generation part 11, the process of the raw material which consists of (2-1) pre-processing process and (2-2) ethanol fermentation process, for example is carried out. Do. The pretreatment step (2-1) includes (2-1-1) a heat treatment step, (2-1-2) an enzyme treatment step, and (2-1-3) a pH adjustment step. Each step will be described below.
[0043]
(2-1) Pretreatment process
(2-1-1) Heat treatment process
Appropriate amount (for example, double amount) of water is added to the apple pomace to make it fluid, and boiled at 100 ° C. for 30 minutes, for example.
[0044]
(2-1-2) Enzyme treatment process
Enzyme treatment is performed by adding an enzyme that increases glucose. As the enzyme, a commercially available appropriate one such as a fibrinolytic enzyme is used.
For example, treatment is performed at 40 ° C. for 24 hours using a stirrer at a speed of 200 rpm, and the amount of glucose produced in the enzyme treatment is, for example, 2820 mg / l.
Thereafter, for inactivation of the enzyme, for example, treatment at 120 ° C. for 10 minutes may be performed.
[0045]
(2-1-3) pH adjustment step
For example, sodium bicarbonate is used to adjust the pH to 5.0 to 8.0, preferably 7.0 ± 0.5.
[0046]
(2-2) Ethanol fermentation process
In this process, as a microorganism, for example, Candida Shahatae deposited at the Patent Biological Depositary Center of the Biotechnology Institute of Industrial Technology, Ministry of Economy, Trade and Industry as deposit number “FERM P-18829” The mutant Candida Shehatae HYO-503 strain is used.
The inoculum amount of Candida Shehatae HYO-503 strain is, for example, 1 × 10^Five This is inoculated as / ml, and the culture temperature is set to 20 ° C. to 37 ° C., for example, 30 ° C., and anaerobic culture is performed for 13 days with carbon dioxide blowing in some cases.
[0047]
Next, when ethanol fermentation is completed, as shown in FIGS. 2 and 4, the raw material is fed to the acetic acid fermentation tank 21 by the pump 16. In this acetic acid fermenter 21, for example, an inoculum of acetic acid bacteria for acetic acid fermentation is 1 × 10⁶ Inoculate to adjust to / ml, inoculate constantly, and perform fermentation at a temperature of 25 ° C. for 14 days.
Then, when the fermentation process is completed, the raw material is conveyed to the centrifuge 30 by the pump 26 as shown in FIGS. Thus, the centrifuge 30 is centrifuged to extract acetic acid. The extracted acetic acid is stored in the acetic acid storage tank 31.
[0048]
(3) Acetic acid mixing step
And as shown in FIG.2 and FIG.6, it processes with the calcium acetate manufacturing apparatus 40. FIG. In this case, calcium carbonate and / or calcium oxide powder particles are conveyed and fed from the hopper 42 into the mixing mixer 41, while acetic acid is supplied from the acetic acid storage tank 31 by the pump 34. In the mixing mixer 41, acetic acid is injected, and the calcium carbonate and / or calcium oxide powder and acetic acid are stirred, thereby reacting with each other to produce a calcium acetate solution.
[0049]
In this acetic acid mixing step, 750 ml of acetic acid having a concentration of 18 to 40% by mass is mixed with 100 g of calcium carbonate and / or calcium oxide so that the amount of calcium acetate is 30% by mass or less. Desirably, the concentration of the acetic acid to be mixed is 20 to 30% by mass, and more desirably 27 ± 1% by mass.
[0050]
Moreover, in the feed production apparatus 50, as shown in FIG.2 and FIG.7, the remaining residue which isolate | separated the acetic acid with the centrifuge 30 is conveyed to the dryer 51, and drying is performed. By this drying, a residue is generated as feed.
[0051]
(4) Adjustment process
Finally, as shown in FIGS. 2 and 8, in the adjustment device 60, water, acetic acid, potassium hydroxide, and glycerin are added to the solution produced by the calcium acetate production device 40 and stirred while heating. In this adjustment step, potassium hydroxide is added in an amount of equimolar or more with respect to 1 mol of unreacted acetic acid in the solution, and the pH of the solution after the addition is in the range of 6.5 to 9.0. . Water, acetic acid, and potassium hydroxide are added according to the following calculation formula so that potassium acetate is added in the solubility limit amount.
[0052]
That is, water, acetic acid, and potassium hydroxide are added according to the formula for calculating the amount of antifreezing agent (B) listed below.
B = A + X (KOH) + Y (water) + Z (CH_ThreeCOOH)
here
B: Production amount (mass) of antifreezing agent
A: Amount (mass) of the solution produced in the acetic acid mixing step
X: KOH amount (mass) of (0.20 to 0.35) times the mass of A solution
Y: Amount of water (mass) that is (0.50 to 0.80) times the mass of solution A
Z: The amount (mass) of acetic acid (0.10 to 0.20) times the mass of the solution A.
[0053]
Preferably
X: KOH amount (mass) of (0.23 to 0.30) times the mass of A solution
Y: Amount of water (mass) that is (0.51 to 0.70) times the mass of solution A
Z: It is the amount (mass) of acetic acid (0.13-0.17) times the mass of A solution.
Most preferably
X: KOH amount (mass) of (0.25 to 0.28) times the mass of the A solution
Y: Amount of water (mass) that is (0.585 to 0.65) times the mass of solution A
Z: The amount (mass) of acetic acid (0.15 to 0.16) times the mass of the A solution.
[0054]
For example, when producing the antifreezing agent (B) that adjusts the pH of the final antifreezing agent to 8.1, it was set as follows.
A: Solution (mass) obtained in the reaction step (reaction carried out at a ratio of 7.5 times the 27% acetic acid solution to the scallop shell mass)
X: KOH amount (mass) of (0.278) times the mass of the A solution
Y: Water amount (mass) of (0.585) times the mass of the A solution
Z: The amount (mass) of acetic acid (0.151) times the mass of the solution A.
[0055]
[Experimental example]
Next, experimental examples will be described.
(Experiment 1) Experiment on optimum reaction conditions between scallop shell and acetic acid
First, experiments were conducted on the optimum conditions for the reaction process for efficiently producing calcium acetate (freezing agent) by the reaction of scallop shell and acetic acid.
[0056]
(Experimental Example 1-1) Relationship between scallop firing temperature and calcium acetate formation reaction
After reacting 100g of scallop shell powders and calcined temperatures of 300 ° C, 400 ° C, 500 ° C, 650 ° C, 850 ° C and 1000 ° C with 27% acetic acid at room temperature for 24 hours, filtration (No1 Toyo Roshi Kaisha, Tokyo) ) To obtain a supernatant and a solid residue. The odor during the reaction, the specific gravity of the liquid after completion of the reaction, and the amount of solid residue were measured. The results are shown in FIG.
[0057]
From the results, during the reaction, the odor after the reaction was observed between the unsintered shell powder and 300 ° C., and the rot odor peculiar to the scallop shell was recognized. In the range of 650 ° C. to 1000 ° C., a sulfur odor was observed during the reaction, but at the end of the reaction for 24 hours, the sulfur odor disappeared. Moreover, remarkable foam was generated during the reaction, and an antifoaming agent (KM72, food additive silicone resin preparation, manufactured by Shin-Etsu Silicone Co., Ltd.) was required. The amount of residue after the reaction was as shown in FIG. The supernatant was yellow in the reaction solution using unsintered powder, 300 ° C to 500 ° C was brownish yellow, and transparent from 650 ° C or higher.
[0058]
From the above results, the reactivity with acetic acid is improved at 500 ° C. or higher. If the temperature exceeds 800 ° C., the reactivity is improved, but the energy consumption increases in the baking process of the scallop shell, and the cost increases. Therefore, it is effective to set the firing temperature of the granular material to 600 ° C to 800 ° C. More preferably, it is effective to set the temperature to 650 ° C. ± 20 ° C. Satisfactory reactivity can be maintained and it is not expensive, so it can be said that the economy is good.
[0059]
(Experimental example 1-2) Relationship between scallop shell amount, acetic acid concentration and acetic acid amount
750 ml of acetic acid solution having a concentration in the range of 2 to 60% by mass and 100 g of scallop shell baked at 650 ° C. were stirred for 24 hours. The residue after the reaction at that time was measured. The comparison result is shown in FIG.
[0060]
From the above results, it can be seen that it is effective to mix 750 ml of acetic acid having a concentration of 18 to 40% by mass with respect to 100 g of scallops. Desirably, the concentration of the acetic acid to be mixed is 20 to 30% by mass, and more desirably 27 ± 1% by mass.
[0061]
(Experimental Example 1-3) Reaction time and amount of residue after reaction
Residues after the reaction were measured with 450 ml of a 27% by mass acetic acid solution and 60 g of 650 ° C. baked scallop shells with the reaction time being changed to 3 hours, 6 hours, 12 hours, and 24 hours. The reaction was 3.95 g at the third hour, 2.05 g at 6 hours, 2.04 g at 9 hours, and 2.01 g at 24 hours.
[0062]
From the above results, the reaction time was 3 hours and the scallop shell residue was 2.95%, 6 hours 2.05%, 9 hours 2.04%, 24 hours 2.01%, and more than 6 hours Since the shell residue showed almost a constant value in the reaction time, it can be seen that the reaction time of 6 to 24 hours is sufficient. More preferably, considering the production efficiency and the calcium content of the scallop shell (calcium carbonate 94.8%), it is appropriate to set the reaction time to 6 hours.
[0063]
(Experimental example 2) Antifreezing effect and melting ice effect of liquid calcium acetate
Prepare a 2-fold dilution series of liquid calcium acetate prepared with 450 ml of 27 mass% acetic acid solution and 60 g of baked scallop shell (650 ° C.) and adjusted to pH 7.0 with 40 mass% KOH, and have an antifreezing effect of −10 The freezing condition was observed by leaving it in a freezing thermostatic chamber at -5 ° C for 24 hours. Freezing protection was observed up to 4 times dilution at -10 ° C and 32 times dilution at -5 ° C, and the ice melting effect was 50.53 mass% at -5 ° C and 10.13 mass% at -10 ° C. . The results are shown in FIG.
[0064]
From this result, the anti-freezing effect of the calcium acetate solution is recognized up to 4-fold dilution at -10 ° C, and up to 32-fold dilution at -5 ° C. The antifreeze is used in the temperature zone of -5 ° C. However, it seems more appropriate than -10 ° C. However, since a 4-fold dilution was observed even at −10 ° C., it can be used as an antifreeze agent by appropriately increasing the amount used. On the other hand, the ice melting effect was found to be 50.53% by mass in the stock solution at −5 ° C. and 10.13% by mass at −10 ° C. Therefore, the antifreezing agent is more at −5 ° C. than at −10 ° C. Also, a high ice melting effect is recognized.
[0065]
(Experimental example 3) Freezing prevention effect and ice melting effect in a mixed solution of calcium acetate and potassium acetate
A two-fold dilution series of 30% by mass calcium acetate solution and 90% by mass potassium acetate solution prepared from scallop shells was prepared, and each equal amount mixed solution was allowed to stand in a -10 ° C freezing thermostat for 24 hours. The frozen state was observed. In addition, the ice melting effect was observed in a frozen thermostat at -5 ° C. for 24 hours, and the ice melting state was observed. The results are shown in FIGS.
When an equal amount of a 90 mass% potassium acetate stock solution to a 64-fold diluted concentration solution was added to a calcium acetate solution stock solution to a 2-fold diluted concentration solution, the antifreezing effect was exhibited more than the calcium acetate single solution.
The ice melting effect was 14.30% by mass when tap water was added to the calcium acetate single solution, but when potassium acetate was added, it was proportional to the dilution factor of 1.30% by mass. It showed 23-61.67 mass%. Further, in the case of potassium acetate single solution, 25.37% by mass in the 4-fold dilution series and no ice-melting effect was observed at 8-fold dilution or more, but when the potassium acetate stock solution was added to the calcium acetate single solution, 61 An ice melting effect of .67% by mass was observed.
[0066]
From the above results, adding potassium acetate to a calcium acetate single solution is an experimental result showing the effect of enhancing the antifreezing effect or the ice melting effect, and the method for producing a liquid antifreeze in this patent application is significant. This is an experimental example to prove that.
[0067]
(Experimental example 4) Comparison of anti-freezing and melting effect of liquid anti-freezing agent prepared in this step and commercial product
Namely, 450 ml of 27% by mass acetic acid solution and 60 g of calcined scallop shell (650 ° C.) were continuously stirred for 6 hours, and the ratio of 71.8 g of acetic acid, 278.1 g of water and 132.2 g of potassium hydroxide to the reaction solution Using a liquid antifreeze agent with a specific gravity of 1.172 and pH 8.1 containing glycerin at a ratio of 7% by mass as a thickener, the antifreeze effect and melting at −5 ° C. The ice effect was observed. The result is shown in FIG.
[0068]
From the above results, the present liquid antifreeze agent has an antifreeze effect equivalent to or better than that of commercially available potassium acetate-based liquid antifreeze agents. Although the value was higher than that of the antifreezing agent, a thin concentration (when used after diluting) shows a high value of the ice melting effect of the liquid antifreezing agent of the present invention. This is presumed to be due to preventing refreezing after melting of ice, and this is characterized in that the antifreezing agent of the present invention has this advantage.
[0069]
(Experimental example 5) Acetic acid odor removal method and apple odor addition
(Experimental example 5-1) Acetic acid odor and pH
By stirring and reacting the baked scallop shell (650 ° C.) and a 27% by mass acetic acid solution for 24 hours, the acetic acid odor and pH of the supernatant solution (calcium acetate solution) after filtration were observed and measured, and by adding 40% by mass KOH The effect of pH change on acetic acid odor was investigated. As a result, no acetic acid odor was observed when the pH was adjusted to 6.4 or higher.
[0070]
(Experimental example 5-2) Addition of apple odor of prepared calcium acetate solution
Apple flavoring for food additives (water-soluble and oily) prepared for anti-freezing agents was added, and the odor of the apple odor and the transition in storage period were examined. The oily apple flavor was able to give a light apple odor by adding 0.02 μg / ml, and the odor was maintained for 6 months.
[0071]
From the above results, an optimum example was found regarding the production of the liquid antifreeze agent. That is, as a result of considering the reaction between scallop shells and acetic acid, antifreezing and ice melting effects, and energy-saving production technology, baked scallop shells (650 ° C.) and 450% of 27 mass% acetic acid were continuously stirred for 6 hours. By adding 278.1 ml of water, 71.8 g of acetic acid and 132.2 g of KOH, and appropriately adding 67.0 g of glycerin and apple flavor to the supernatant solution after filtration, a liquid cryoprotectant (pH 8.1, specific gravity 1.172). )
[0072]
Specifically, in order to efficiently produce a liquid antifreeze (calcium acetate) from scallop shells and acetic acid, basic reaction conditions for the reaction process must be established. The requirements are (1) easy reaction process, (2) less reaction time and residue after reaction, (3) minimum amount of acetic acid, (4) high solubility of calcium acetate, (5) simplification of process. And (6) Freezing prevention and a large melting effect can be considered.
[0073]
In the present invention, in consideration of these requirements, in the calcium acetate production process using scallop shell as a raw material, the relationship between the size and reaction of scallop shell, which is the first step, can reduce the firing rate if the crushed particle size is reduced. As predicted, it is speculated that making the particle size smaller than the pulverized particle size would increase the cost of the pulverizer, and this pulverized particle size is considered appropriate in terms of equipment costs. A reaction process is obtained in which the crushed scallop shell is fired at 650 ° C. and a certain amount thereof is reacted with 7.5 mass of 27% by mass acetic acid. This is because the main component of scallop shell is 94.8% by mass of calcium carbonate. In order to save calcium acetate energy-saving by reaction with acetic acid, it can be crushed or not crushed. It is not necessary and is thought to lead to cost savings. However, the crushed scallop shell powder that is not baked is inefficient because it has a rot odor and a large amount of residue due to reaction with acetic acid for 24 hours, and there are many unreacted scallop shells. Accordingly, a firing step around 650 ° C. is appropriate because of the expense required for firing, shortening of the reaction time, and little residue after the reaction. Around 650 ° C. is a temperature zone in which generation of dioxins must be considered.
[0074]
In the composition analysis by X-ray energy dispersion of scallop shells not listed above, calcium, phosphorus and carbon are almost all and the chloride content is extremely small, but it is also derived from marine products, so that concern needs to be considered. From the composition analysis of the scallop shell, it is considered that the residue after the reaction is generated in the range of 3 to 6% by mass even after the firing step. It is thought that the fact that the elemental component of the residue has a high carbon ratio is derived from a component that does not participate in the calcium acetate formation reaction.
[0075]
When the antifreezing effect and the ice melting effect in the solution of each of calcium acetate and potassium acetate are compared with respect to the liquid antifreeze agent, almost the same effect is shown. In particular, in the ice melting effect, a mixed solution of a calcium acetate stock solution series and a potassium acetate diluted series shows a higher melting effect than a single series solution. This is not simply caused by the increase in the molar concentration of the salt, but is presumed to be due to the mutual state change of the mixed solution. The proof of this phenomenon is thought to be clarified by measuring the freezing point depression. In any case, it is considered that these results can keep the concentration of expensive potassium acetate low, and can obtain the antifreezing effect and the melting effect as low as potassium acetate. In addition, it is considered that a mixed solution of potassium acetate would be meaningful because it is difficult to obtain a molar concentration of 35% by mass or more due to the chemical properties of calcium acetate.
[0076]
Regarding the method of removing acetic acid odor, which is a drawback of acetic acid-type antifreezing agents, it is possible to remove potassium acetate with unreacted acetic acid and produce potassium acetate with a high melting effect by adjusting the pH using potassium hydroxide. It has the advantage that it can be easily prepared with a mixture of calcium acetate and potassium acetate.
[0077]
Moreover, since the point which adds an apple odor to a liquid freezing inhibitor uses the acetic acid derived from an apple pomace, it could have an apple odor inevitably.
The establishment of an efficient reaction production process for producing calcium acetate-based antifreezing agents with scallop shells and acetic acid has solved the main problems of the production process technology from raw materials to products.
[0078]
【The invention's effect】
  As explained above, the present inventionManufactured by liquid antifreeze manufacturing methodAccording to the liquid antifreeze agent, the ice melting effect is improved because calcium acetate is mixed with potassium acetate in a state in which the dissolution rate is kept high, thereby forming a liquid state. Thereby, spreading becomes easy and the immediate effect of melting ice is achieved. In addition, although potassium acetate is expensive, potassium acetate is added in a state that keeps it in a liquid state at a minimum, and an antifreezing agent having a higher melting effect than calcium acetate is manufactured as cheaply as possible. become able to.
[0079]
Further, according to the method for producing a liquid antifreezing agent of the present invention, in the acetic acid mixing step, 750 ml of acetic acid having a concentration of 18 to 40% by mass is mixed with 100 g of calcium carbonate and / or calcium oxide, and the amount of calcium acetate Is produced so that the solubility of 30% by mass or less is not practically precipitated from conditions such as outside air temperature or room temperature, so that precipitation is prevented. The dissolution rate can be as high as possible. Therefore, it is possible to manufacture the antifreezing agent as inexpensively as possible, and it is possible to facilitate the application of the melted ice by facilitating spraying.
[0080]
Further, in the adjusting step, potassium hydroxide is added in an amount of equimolar or more and 1 mol of unreacted acetic acid in the solution, and the pH of the solution after the addition is in the range of 6.5 to 9.0. When configured, potassium acetate is generated and can be mixed with calcium acetate to form a liquid state. Therefore, with calcium acetate alone, the melting concentration is about 30% by mass, so that the ice melting effect is limited. However, the mixing of potassium acetate can improve the ice melting effect. Also. Potassium acetate is added in a state in which the liquid state is kept to a minimum, and an antifreezing agent having a higher ice melting effect than calcium acetate can be produced as cheaply as possible.
[Brief description of the drawings]
FIG. 1 is a process diagram showing a method for producing a liquid antifreeze agent according to an embodiment of the present invention.
FIG. 2 is an overall view showing a manufacturing apparatus that realizes a method for manufacturing a liquid cryoprotectant according to an embodiment of the present invention.
FIG. 3 is a diagram showing a configuration of a calcium production apparatus in a production apparatus that realizes a method for producing a liquid cryoprotectant according to an embodiment of the present invention.
FIG. 4 is a diagram showing a configuration of an ethanol generation unit and a part of an acetic acid generation unit of an acetic acid production apparatus in a production apparatus that realizes the method for producing a liquid cryoprotectant according to an embodiment of the present invention.
FIG. 5 is a diagram showing a partial configuration of an acetic acid production unit of an acetic acid production apparatus in a production apparatus that realizes the method for producing a liquid cryoprotectant according to an embodiment of the present invention.
FIG. 6 is a diagram showing a configuration of a calcium acetate production apparatus in a production apparatus that realizes the method for producing a liquid cryoprotectant according to an embodiment of the present invention.
FIG. 7 is a diagram showing a configuration of a feed production apparatus in a production apparatus that realizes the method for producing a liquid cryoprotectant according to an embodiment of the present invention.
FIG. 8 is a diagram showing a configuration of an adjusting device in a manufacturing apparatus that realizes a manufacturing method of a liquid antifreeze agent according to an embodiment of the present invention.
FIG. 9 is a table showing the influence of the calcination temperature of scallop shells on the calcium acetate production reaction according to an experimental example of the present invention.
FIG. 10 is a table showing the relationship between the amount of scallops, the amount of acetic acid, and the concentration according to an experimental example of the present invention.
FIG. 11 is a table showing anti-freezing and a melting effect of a calcium acetate solution according to an experimental example of the present invention.
FIG. 12 is a table showing the antifreezing effect of a mixed solution of calcium acetate and potassium acetate according to an experimental example of the present invention.
FIG. 13 is a table showing the ice melting rate of a mixed solution of calcium acetate and potassium acetate according to an experimental example of the present invention.
FIG. 14 is a table showing a comparison between the antifreezing effect and the ice melting effect of a liquid antifreezing agent and a commercially available product according to an experimental example of the present invention.
[Explanation of symbols]
(1) Calcium production process
(2) Acetic acid production process
(2-1) Pretreatment process
(2-2) Ethanol fermentation process
(3) Acetic acid mixing step
(4) Adjustment process
1 Calcium production equipment
7 Baking machine
10 Acetic acid production equipment
11 Ethanol generator
12 Ethanol fermentation tank
20 Acetic acid generator
21 Acetic acid fermenter
30 Centrifuge
31 Acetic acid storage tank
40 Calcium acetate production equipment
50 Feed production equipment
60 Adjustment device

Claims (22)

In a method for producing a liquid antifreeze, the method comprises an acetic acid mixing step of mixing calcium carbonate and / or calcium oxide and acetic acid, and producing a liquid antifreezing agent containing calcium acetate by mixing acetic acid in the acetic acid mixing step.
In the acetic acid mixing step, 750 ml of acetic acid having a concentration of 18 to 40% by mass is mixed with 100 g of calcium carbonate and / or calcium oxide, and the amount of calcium acetate is 30% by mass or less .
An adjustment step for adjusting the solution produced in the acetic acid mixing step is provided, and in the adjustment step, potassium hydroxide is equimolar or more with respect to 1 mol of unreacted acetic acid in the solution, and the pH of the solution after addition Is added so as to be in the range of 6.5 to 9.0 . The method for producing a liquid antifreeze according to claim 1 , wherein the concentration of the acetic acid to be mixed is 20 to 30% by mass. The method for producing a liquid antifreeze according to claim 2 , wherein the concentration of the acetic acid to be mixed is 27 ± 1% by mass. The method for producing a liquid antifreeze according to any one of claims 1 to 3, wherein potassium acetate is added in a solubility limit amount. 5. The method for producing a liquid antifreeze according to claim 4 , wherein water, acetic acid and potassium hydroxide are added. 6. The method for producing a liquid antifreeze according to claim 5 , wherein water, acetic acid, and potassium hydroxide are added according to a calculation formula for the amount (B) of the antifreeze produced below.
B = A + X (KOH) + Y (water) + Z (CH ₃ COOH)
Where B: Amount of antifreeze produced (mass)
A: Amount (mass) of the solution produced in the acetic acid mixing step
X: KOH amount (mass) of (0.20 to 0.35) times the mass of A solution
Y: Amount of water (mass) that is (0.50 to 0.80) times the mass of solution A
Z: The amount (mass) of acetic acid (0.10 to 0.20) times the mass of the solution A. Glycerin is added, The manufacturing method of the liquid antifreezing agent in any one of the Claims 1 thru | or 6 characterized by the above-mentioned . The method for producing a liquid antifreeze according to any one of claims 1 to 7 , wherein a fragrance is imparted. An acetic acid production process for producing acetic acid to be used as a raw material waste is provided. In the acetic acid production process, apple squeezed rice cake is used as the fruit and vegetable waste, and apple aroma is added to the produced acetic acid. The method for producing a liquid antifreeze according to claim 8 . A calcium production process for producing calcium carbonate and / or calcium oxide to be used as a raw material, wherein the shell is washed, the washed shell is crushed, and the pulverized powder is obtained. The method for producing a liquid antifreeze according to any one of claims 1 to 9, wherein calcium carbonate and / or calcium oxide is produced by firing. The method for producing a liquid antifreeze according to claim 10 , wherein the firing temperature of the granular material is 500 ° C. or higher. The method for producing a liquid antifreeze according to claim 11 , wherein a firing temperature of the granular material is 600 ° C. to 800 ° C. 13. The method for producing a liquid antifreeze according to claim 12 , wherein the firing temperature of the granular material is 650 ° C. ± 20 ° C. The method for producing a liquid antifreeze according to any one of claims 10 to 13 , wherein a scallop shell is used as the shell. Liquid freeze protection comprising calcium acetate by mixing with acetic acid in which calcium carbonate and / or calcium oxide and acetic acid are mixed, and mixing acetic acid in the acetic acid mixing step In the method for producing a liquid antifreeze agent for producing a stopper,
  In the acetic acid mixing step, 750 ml of acetic acid having a concentration of 18 to 40% by mass is mixed with 100 g of calcium carbonate and / or calcium oxide, and the amount of calcium acetate is 30% by mass or less.
  A calcium production process for producing calcium carbonate and / or calcium oxide to be used as a raw material for the shell, in which the shell is washed, the washed shell is crushed, and the crushed powder A method for producing a liquid antifreeze, characterized in that calcium carbonate and / or calcium oxide is produced by firing, and the firing temperature of the powder is set to 500 ° C. or higher. The method for producing a liquid antifreeze according to claim 15, wherein the concentration of the acetic acid to be mixed is 20 to 30% by mass. The method for producing a liquid antifreeze according to claim 16, wherein the concentration of the acetic acid to be mixed is 27 ± 1% by mass. The method for producing a liquid antifreeze according to any one of claims 15 to 17, wherein a fragrance is imparted. An acetic acid production process for producing acetic acid to be used as a raw material waste is provided. In the acetic acid production process, apple squeezed rice cake is used as the fruit and vegetable waste, and the aroma of apple is added to the produced acetic acid. The method for producing a liquid antifreeze according to claim 18. The method for producing a liquid antifreeze according to any one of claims 15 to 19, wherein the powder is fired at a temperature of 600 ° C to 800 ° C. 21. The method for producing a liquid antifreeze according to claim 20, wherein the firing temperature of the granular material is 650 ° C. ± 20 ° C. The method for producing a liquid antifreeze according to any one of claims 15 to 21, wherein a scallop shell is used as the shell.

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