KR100753357B1 - Manufacturing Method and Equipment of Dietary Sulfur - Google Patents

Abstract

It is for producing plant-derived dietary sulfur through chemical reaction of lignin component which removes fiber, cellulose and semi cellulose generated during the papermaking process of making pulp out of wood and acts as a binder of remaining fiber. The primary oxidation process for oxidizing the contained material by hydrogen peroxide above 85 ℃, the cooling process for cooling the primary oxidized material below 60 ℃, the pH adjustment process for adjusting to pH of neutral zone, and the pH adjustment Provided is a method for producing dietary sulfur comprising a secondary oxidation process of oxidizing a substance through ozone and a crystallization process of cooling the secondary oxidized substance to 0 to 15 ° C. for crystallization.

Dietary sulfur, lignin, lignosulfonate, papermaking process, by-products, fiber, oxidation, hydrogen peroxide, ozone

Description

Manufacturing Method and Equipment of Dietary Sulfur {Manufacturing Method and Equipment of Dietary Sulfur}

1 is a block diagram showing an embodiment of a dietary sulfur production apparatus according to the present invention.

Figure 2 is a graph showing the results of quantitative analysis by gas chromatography the content of the intermediate product obtained from the primary oxidizer while changing the reaction temperature in one embodiment of the dietary sulfur production apparatus according to the present invention.

Figure 3 is a graph measuring the efficiency of the secondary oxidation reaction by ozone in accordance with the pH change in one embodiment of the dietary sulfur production apparatus according to the present invention.

Figure 4 is a graph measuring the efficiency of the secondary oxidation reaction by ozone while changing the reaction temperature in one embodiment of the dietary sulfur production apparatus according to the present invention.

5 is a graph measuring the efficiency of the secondary oxidation reaction by ozone while changing the supply amount of ozone in one embodiment of the dietary sulfur production apparatus according to the present invention.

The present invention relates to a method and a manufacturing apparatus for dietary sulfur, and more particularly, to the primary oxidation process by hydrogen peroxide from the by-products of the papermaking process, the cooling process, adjusting the pH of the neutral zone, the secondary oxidation process through ozone, cooling The present invention relates to a method for producing dietary sulfur and an apparatus capable of effectively separating dietary sulfur through crystallization.

In general, Lignosulfonate, a by-product generated during the papermaking process, is known as the main raw material of dietary sulfur derived from plants.

Looking at the human usefulness of dietary sulfur, sulfur is the third most abundant mineral in our body after calcium and phosphorus, and adults have about 140g of sulfur in our body, and nearly half of it is present in muscle, skin and bone. . Animals also consume crystalline organic sulfur to produce methionine and cysteine, which are sulfur-containing essential amino acids. Cysteine has a sulfur (-S-S-) bond and is a substance that determines the protein's biological structure and properties by determining the tertiary structure of the protein. The protein tertiary structure of crystalline organic sulfur (methylsulfonylmethane) improves the permeability of the cell membrane, aids in the absorption of nutrients and removes waste. In addition, the release of toxic substances and the supply of nutrients in the joints contribute to joint health. In cartilage, glucosamine and chondrin, sulfur-containing proteoglycans, combine with collagen to give cartilage flexibility. The supply of organic sulfur plays a major role in the production of glucosamine and chondroitin containing sulfur, which is a component of cartilage, and helps joint health by having an effect against inflammation.

Therefore, it is a very useful technique to effectively separate dietary sulfur which is useful for human body from by-products generated during the papermaking process.

However, some methods have been proposed to treat lignosulfonate, a by-product generated during the papermaking process, for the production of dietary sulfur.

Commonly used methods include (1) decomposition of by-products by oxidation treatment under high temperature and high pressure, (2) decomposition of by-products by ultraviolet irradiation under alkaline conditions, and (3) oxidation of by-products by addition of hydrogen peroxide. And the like are known.

However, the oxidation of the by-products by the method of (1) has a problem inherent in the difficulty of manufacturing the equipment and the risk of high temperature and high pressure. In addition, in the method (2), the oxidation treatment by ultraviolet irradiation has a problem that the production efficiency of dietary sulfur is not good because the cost and processing speed are rather slow. In addition, the method of (3) has a problem in the process of repeating the purification of dietary sulfur, that is, distillation and purification several times as a method used as a general oxidation process.

The present invention is a primary oxidation process by hydrogen peroxide, cooling process, adjusting to the pH of the neutral region, secondary oxidation process through ozone, cooling to crystallize so as to effectively separate the dietary sulfur from lignosulfonate It is an object of the present invention to provide a low-cost and high-efficiency dietary sulfur production method.

And another object of the present invention is to provide a dietary sulfur production apparatus that can be produced by effectively separating the dietary sulfur useful in the human body from lignosulfonate.

The method for producing dietary sulfur proposed by the present invention includes a first oxidation process for oxidizing lignosulfonate-containing material by hydrogen peroxide at 85 ° C. or higher, a cooling step for cooling the primary oxidized material to 60 ° C. or lower, PH adjustment process for adjusting the pH of the neutral region, secondary oxidation process for oxidizing the pH adjusted material through ozone, and crystallization process for crystallizing the secondary oxidized material by cooling it to 0-15 占 폚. .

The lignosulfonate-containing material may be used as a lignin component that serves as a binder of the remaining fibers to remove the fibers, cellulose and semi-cellulose generated during the papermaking process made of wood pulp.

As described above, when the first oxidation process by hydrogen peroxide and the second oxidation process by ozone addition are performed under optimal pH conditions, it is possible to produce dietary sulfur sufficiently and quickly and efficiently and inexpensively.

In the secondary oxidation process, it is preferable to perform degassing to promote the dissolution of ozone. When degassing as described above, dissolved oxygen and the like during the secondary oxidation process are reduced, so that the added ozone is efficiently and quickly dissolved, and the efficiency of the oxidation process by ozone addition is further increased.

By measuring the exhaust ozone concentration exhausted under the known addition ozone concentration in the secondary oxidation process, it is possible to determine the end point of the oxidation reaction from the change of the exhaust ozone concentration. That is, when most of the substances to be treated are oxidized, the consumption of ozone to be added is almost eliminated, and the concentration of the exhausted ozone gas becomes almost constant, and it is possible to confirm whether or not the oxidation reaction has been substantially terminated from the change in concentration. In addition, it is possible to save the amount of ozone by stopping the addition of ozone.

Maintaining the temperature above 85 ° C. in the primary oxidation process is preferable because the oxidation reaction by hydrogen peroxide is smoothly performed.

Maintaining the temperature in the primary oxidation process within about 110 ° C. is advantageous in terms of energy consumption and smooth oxidation reaction for maintaining the temperature.

Hydrogen peroxide used in the primary oxidation process is used as a solution in the range of about 30 to 80%.

If the concentration of the hydrogen peroxide solution is too thin, it takes a long time to complete the oxidation reaction, if too thick there is a problem that excessive oxidation occurs or some of the hydrogen peroxide is not involved in the oxidation reaction is wasted.

And the theoretical requirement of hydrogen peroxide to oxidize lignosulfonate in the first oxidation process is determined by stoichiometric molar ratio.

That is, hydrogen peroxide is required to oxidize 100 mg / L lignosulfonate because the amount of hydrogen peroxide is required per 1 mole of oxygen generated by the oxidation reaction of hydrogen peroxide (2H ₂ O ₂ → 2H ₂ O + O ₂ ). mg / L is required.

Therefore, the amount of hydrogen peroxide added during the first oxidation process is determined by the amount of lignosulfonate for oxidation treatment, and the amount of hydrogen peroxide solution is determined by the concentration of hydrogen peroxide. For example, when a 50% hydrogen peroxide solution is used, the volume of the lignosulfonate for the oxidation treatment: the volume of the hydrogen peroxide solution is set at about 1: 4.

In the cooling process, it is possible to precipitate some of the dietary sulfur generated by oxidation of lignosulfonate by cooling the temperature maintained at 85 ° C. or higher in the first oxidation process to 60 ° C. or lower.

If the cooling temperature is set too low in the above, secondary oxidation is not performed smoothly. Therefore, the cooling temperature in the cooling process is preferably set to about 25 ℃ or more because the secondary oxidation is effective.

In the pH correction process, the pH is adjusted to a neutral region (for example, a neutral region of pH 6.9 to 7.1) using an artificial method such as sodium hydroxide (NaOH) or an acid such as sulfuric acid (H ₂ SO ₄ ). .

As described above, if pH is corrected to the neutral region before being introduced into the secondary oxidation process, the reaction efficiency is greatly improved during the secondary oxidation process.

In the secondary oxidation process, since the oxidation reaction proceeds in proportion to the amount of ozone added, it is preferable to perform degassing of dissolved oxygen or the like to improve the solubility of ozone.

In the case of continuously injecting a certain amount of ozone in the secondary oxidation process, the amount of exhaust ozone that is exhausted also increases, and the rate at which the amount of exhaust ozone increases is substantially lowered and gradually stops as the end point of the oxidation reaction approaches. Therefore, it is possible to stop the addition of unnecessary ozone, thereby enabling proper use of ozone.

When the second oxidation is completed in the crystallization process is cooled to about 0 ~ 15 ℃, dietary sulfur is precipitated is obtained.

In the method for producing dietary sulfur of the present invention, the lignosulfonate-containing material is subjected to primary oxidation with hydrogen peroxide at 85 ° C. or higher, and the primary oxidized material is cooled to 0 to 15 ° C. for crystallization, followed by centrifugation. It is also possible to repeat the process of filtrating the filtrate at 85 ° C. or higher by primary oxidation with hydrogen peroxide and cooling to 0 to 15 ° C. for crystallization.

In addition, the method for preparing dietary sulfur of the present invention adjusts the material containing lignosulfonate to the pH of the neutral region in the range of pH 6.9 to 7.1, oxidizes the pH-adjusted material through ozone, and oxidizes the oxidized material to 0 to It is also possible to comprise a process of crystallizing by cooling to 15 ℃.

In addition, the dietary sulfur production apparatus of the present invention is a separation device for producing and processing the by-product containing lignosulfonate generated during the papermaking process, a storage tank for storing the by-product supplied from the separation device, hydrogen peroxide supply for supplying hydrogen peroxide A primary oxidizer connected to the apparatus and the storage tank to receive a by-product, maintain a reaction temperature at a constant temperature, and supply a hydrogen peroxide from a hydrogen peroxide supply device to perform a primary oxidation reaction, and discharged to the primary oxidizer. A pH correction device for correcting the pH of the substance subjected to the first oxidation reaction, an ozone supply device for generating and supplying ozone, and a pH-corrected material connected to the pH correction device and supplied with ozone from the ozone supply device. And a secondary oxidation device in which the secondary oxidation reaction is supplied.

Next, a preferred embodiment of a dietary sulfur production apparatus according to the present invention will be described in detail with reference to the drawings.

First, an embodiment of the dietary sulfur production apparatus according to the present invention, as shown in Figure 1, the separation device 2, the storage tank 4, the hydrogen peroxide supply device 14, the primary oxidizer 10 And a pH correction device 20, an ozone supply device 42, a secondary oxidation device 40, and the like.

The separator 2 produces and processes by-products containing lignosulfonate generated during the papermaking process.

By-products produced and processed in the separator 2 are sent to the storage tank 4 through a pump 3.

An exhaust pipe 5 is installed above the storage tank 4 to discharge gas generated by opening as needed.

By-products stored in the storage tank 4 are sent to the primary oxidizer 10 via a pump 8 via a transfer line.

The primary oxidizer 10 is connected to the heating device 18 for supplying heat to maintain the temperature above 85 ℃.

For example, the heating device 18 may be configured as a steam supply device for supplying hot steam, or may be configured as a hot water supply device for supplying hot water.

In addition, the primary oxidizer 10 is provided with a heat discharge device 19 for discharging steam or hot water.

 The hydrogen peroxide supply device 14 is installed to supply hydrogen peroxide or a hydrogen peroxide solution to the primary oxidizer 10.

And the primary oxidizer 10 is connected to the oxygen exhaust pipe 16 for discharging the oxygen generated by the oxidation reaction.

The intermediate product produced by the primary oxidation reaction in the primary oxidizer 10 is supplied to the secondary oxidizer 40 through the pump 15.

In order to remove the foreign matter contained in the intermediate product supplied to the secondary oxidizer 40 from the primary oxidizer 10, a filtration device 22 is installed in the transfer line.

In order to adjust the pH of the intermediate product supplied from the primary oxidizer 10 to the secondary oxidizer 40 to the neutral region (adjust to the optimal pH), an acid such as H ₂ SO ₄ or an alkali such as NaOH PH correction device 20 for supplying the is installed connected to the transfer line. Neutral region in the above means a range of pH 6.9 ~ 7.1.

The secondary oxidizer 40 is composed of a vertical reaction column, the lower portion is connected to the ozone supply device 42.

The ozone supply device 42 is connected to an air supply pipe 43 for supplying dry air.

The ozone supply device 42 generates ozone from the supplied dry air and supplies it to the secondary oxidizer 40.

The secondary oxidizer 40 is provided with an ozone exhaust device 46 for discharging excess ozone that does not participate in the reaction in the ozone supplied from the ozone supply device 42.

The ozone exhaust device 46 is connected to an ozone concentration measuring device (not shown) for measuring the concentration of ozone to be exhausted.

The ozone exhaust device 46 can also be used as a degassing device for degassing dissolved oxygen or the like.

The secondary oxidizer 40 is connected to a cooling device 44 for supplying cooling water for cooling.

In the cooling device 44, when the secondary oxidation reaction of the secondary oxidation device 40 is completed, cooling water is supplied to cool the temperature of the secondary oxidation device 40 to 15 ° C. or less.

In addition, the secondary oxidizer 40 is connected to the cooling water discharge device 15 for discharging the supplied cooling water.

The ozone exhaust device 46 may be connected to the cooling water discharge device 15 to discharge the cooling water and the exhaust ozone together.

In the present embodiment, a series of operations of the above apparatus can be configured to be controlled either manually or automatically.

It is also possible to install the control device 50 for the automatic control in the above.

The control device 50 is input to the ozone concentration measuring device installed in the ozone exhaust device 46, the signal from the pH correction device 20, the operating condition set value of each device, if necessary, the heating device ( 18), control signals of the operation pumps 3, 8, 15, pH correction device 20, ozone supply device 42, and the like are output.

Referring to the process of producing dietary sulfur using one embodiment of the dietary sulfur production apparatus according to the present invention configured as described above are as follows.

In the present invention, the basic technical value is to remove the fiber, cellulose and semi-cellulose produced during the paper making process of wood pulp, and to produce dietary sulfur derived from plants through chemical reaction of the lignin component that acts as a binder of the remaining fibers. It is in doing it. In particular, the optimum reaction temperature and reaction conditions are adjusted to allow for the most efficient treatment, while at the same time setting the optimum temperature for each oxidation process, recognizing the end point of the operation and reducing the purity of the plant-derived dietary sulfur. The purpose of the present invention is to enable a combination of improvements such as work time.

First, by supplying the byproduct separated from the fibrous component through the paper mill, the concentration of hydrogen peroxide in the primary oxidizer 10, the volume ratio of the reactants, the optimum reaction temperature and the setting of the cooling temperature through the cooling water supply device 44, optimum The pH conditions, the concentration of the supplied ozone in the secondary oxidizer 40, the setting of the reaction temperature, and the like were carried out.

The primary oxidizer 10 is composed of a pilot device for a capacity of 15 liters, and a hot water supply device is installed as a heating device 18 to continuously supply and circulate hot water having a maximum set temperature of 95 ° C. by providing a circulation device. .

In addition, a hydrogen peroxide supply device 14 is provided, and an oxygen exhaust pipe 16 capable of exhausting the generated oxygen is also provided.

PH correction of the intermediate product subjected to the primary oxidation treatment in the primary oxidizer 10 was performed by an artificial method.

The secondary oxidizer 40 uses a reaction tower having a height of 2.0 m and a capacity of 10 liters.

The secondary oxidizer 40 was provided with a cooling device 44 capable of cooling the temperature to 5 ° C, and an ozone exhaust device 46 was installed to discharge excess ozone and reactive oxygen.

In the above, ozone is generated from the dry air by the ozone supply device 42 and supplied from below the secondary oxidizer 40 at a predetermined constant flow rate.

The intermediate product to be treated in the secondary oxidizer 40 was contacted with ozone supplied from below through the ozone supply device 42 while circulating from the top to the pump 15 in the downward direction.

First, the reaction conditions of the primary oxidation process are confirmed through the proper concentration of hydrogen peroxide, the reaction volume ratio of by-products and hydrogen peroxide, and the reaction temperature in the primary oxidizer 10. The cooling process after the primary oxidation reaction is 25 ° C. and 40 ° C. The temperature was set at 60 ° C. to set the cooling temperature.

The pH correction is performed by artificially using NaOH or H ₂ SO ₄ , and gradually increases the amount of ozone supplied to the secondary oxidizer 40 to reduce the amount of dietary sulfur produced per unit time according to the amount of ozone. Calculated.

Hydrogen peroxide was used as the 50% solution, and the theoretical requirement of hydrogen peroxide for oxidation treatment of lignosulfonate was determined according to the stoichiometric molar ratio related to the concentration of lignosulfonate to be treated.

In other words, in the oxidation reaction (2H ₂ O ₂ → 2H ₂ O + O ₂ ), if 2 moles of hydrogen peroxide is required per mole of oxygen required for the oxidation of lignosulfonate, 100 mg / L of lignosulfonate is removed. The amount of hydrogen peroxide required to achieve this is calculated to be 212.5 mg / L.

Based on the above theoretical requirements, the reaction volume ratio of by-product and hydrogen peroxide can be estimated.The reaction volume ratio of by-product: hydrogen peroxide 50% solution is set to approximately 1: 4, and the reaction time is decomposed by the reaction temperature for the same reaction time. The state is determined as the efficiency of the first oxidation process, and the content of the liquid dietary sulfur, which is an intermediate, is shown in FIG. 2.

Analysis conditions of gas chromatography for the analysis of the intermediate product produced in the first oxidation reaction is set as follows.

Column: HP 19395A

Injection part temperature: 125 ℃

Column temperature: 210 ℃

Detector temperature: 250 ℃

Carrier gas and flow rate: Helm, 10ml / min

Injection volume: 3ml

Detector: Flame photometric detecor (FPD)

As can be seen from Figure 2, the higher the reaction temperature of the primary oxidizer 10, the content of the resulting liquid diet sulfur increases, it is preferable to maintain about 90 ℃ to produce liquid diet sulfur with sufficient efficiency .

3 shows the degree of decomposition of the intermediate product according to the change of pH under a certain amount of ozone inflow during the secondary oxidation reaction.

As confirmed from FIG. 3, the decomposition of the intermediate product was found to be much higher in the reaction efficiency in the neutral region. In other words, the yield was much lower than alkaline treatment at pH9.5 or higher. By oxidizing the intermediate product under such optimum pH conditions, it is possible to carry out the targeted oxidation treatment using the minimum amount of ozone substantially required.

Figure 4 shows the desired reaction temperature at a certain amount of ozone inflow and a proper pH in the secondary oxidation process by ozone. In other words, the treatment characteristics of the intermediate product according to the reaction temperature was significantly improved the efficiency at the reaction temperature of 25 ℃ or more, especially when the reaction at 40 ℃ or more it was confirmed that the effect of reducing the ozone inflow is greater than the room temperature. On the other hand, when the reaction temperature is more than 60 ℃ to 70 ℃ it was confirmed that the reduction effect of the ozone inflow reduced.

Therefore, the temperature of the intermediate product supplied from the primary oxidizer 10 to the secondary oxidizer 40 is preferably cooled to 60 ° C. or lower, and preferably maintained at approximately 25 ° C. or higher.

Figure 5 shows the result of inducing crystallization by cooling to 5 ℃ after the reaction by increasing the ozone addition step by step in order to determine the yield according to the final ozone addition amount.

As can be seen in Figure 5, basically the oxidation reaction proceeds effectively in proportion to the amount of ozone added. Therefore, increasing the solubility of ozone increases the efficiency of the oxidation process, and therefore, it is effective to perform degassing of dissolved oxygen or the like to promote the dissolution of ozone.

In the secondary oxidation process by ozone, the amount of exhaust ozone exhausted also increases when a certain amount of ozone is continuously injected, and the increase substantially stops when the end point of the oxidation reaction is approached. Therefore, it is possible to stop the addition of excess ozone further, so that proper ozone use is possible in this respect.

Analysis conditions of gas chromatography for the analysis of dietary sulfur, which is the final product by the secondary oxidizer 40 is as follows.

Column: BP-20 colume (HP)

Injection part temperature: 160 ℃

Column Temperature: 230 ℃

Detector temperature: 250 ℃

Carrier gas and flow rate: Helm, 30ml / min

Injection volume: 3ml

Detector: Flame photometric detecor (FPD)

Figure 5 shows the analysis of the crystallization of dietary sulfur under the above conditions.

In the above description of the preferred embodiment of the method for producing dietary sulfur and the manufacturing apparatus according to the present invention, the present invention is not limited to this, but the present invention is not limited to the claims and the detailed description of the invention and the various modifications carried out within the scope of the accompanying drawings. It is possible and this also belongs to the scope of the present invention.

According to the dietary sulfur production method and apparatus according to the present invention made as described above, the first oxidation process by hydrogen peroxide and the second oxidation process through ozone to maintain the pH appropriately, very efficiently with a small amount of ozone The oxidation treatment can be carried out to obtain an excellent treatment performance.

In addition, according to the method and manufacturing apparatus for dietary sulfur according to the present invention, it is possible to manufacture dietary sulfur by using a part of the by-products generated during the papermaking process that is discarded as industrial waste, it is very effective in preventing environmental pollution and protecting nature It is also effective in recycling resources.

According to the dietary sulfur production method and apparatus according to the present invention, since the conditions of high temperature and high pressure are not adopted, there is an advantage that it is safe.

According to the method and manufacturing apparatus for dietary sulfur according to the present invention, it is possible to effectively obtain dietary sulfur from the lignosulfonate through the first and second oxidation processes, it is possible to realize high productivity at low cost, It is possible to provide a technology that is practically feasible.

Claims (11)

A primary oxidation process for oxidizing lignosulfonate-containing material by hydrogen peroxide at 85 ° C. or higher, A cooling process of cooling the primary oxidized material to 25 to 60 ° C., pH adjustment process to adjust the pH of the neutral region in the range of pH 6.9 ~ 7.1, a secondary oxidation process for oxidizing the pH adjusted material through ozone, A method for producing dietary sulfur comprising a crystallization process in which the secondary oxidized material is cooled to 0 to 15 ° C. for crystallization. The method according to claim 1, Hydrogen peroxide used in the first oxidation process is used as a solution in the range of 30 to 80%, The use amount of the hydrogen peroxide is set in the range of 1.5 to 2.5 times the amount of lignosulfonate for oxidation treatment. The method according to claim 1, Dietary sulfur production method for setting the cooling temperature to 25 ℃ or more in the cooling process. The method according to claim 1, The material containing lignosulfonate is subjected to primary oxidation by hydrogen peroxide at 85 ° C. or higher, and the primary oxidized material is cooled to 0 to 15 ° C. for crystallization and centrifuged, and the filtrate is hydrogen peroxide at 85 ° C. or higher. A process for producing dietary sulfur comprising repeating a process of primary oxidation by and cooling to 0 to 15 ° C. for crystallization. The method according to claim 1, Dietary sulfur consisting of adjusting the material containing lignosulfonate to pH 6.9 to 7.1 in the neutral region, oxidizing the pH adjusted material through ozone, and cooling the oxidized material to 0 to 15 ° C. Manufacturing method. Separation device for producing and processing byproducts containing lignosulfonate generated during the papermaking process, A storage tank for storing the by-product supplied from the separator, A hydrogen peroxide supply device for supplying hydrogen peroxide, A primary oxidizer connected to the storage tank to receive a by-product, maintain a reaction temperature at a predetermined temperature, and supply a hydrogen peroxide from a hydrogen peroxide supply device to perform a primary oxidation reaction; A pH correction device for correcting the pH of the material subjected to the primary oxidation reaction which is connected to the primary oxidizer and discharged; An ozone supply device for generating and supplying ozone; And a secondary oxidation device connected to the pH correction device and supplied with a pH-corrected material and supplied with ozone from the ozone supply device to perform a secondary oxidation reaction. The method according to claim 6, Dietary sulfur production apparatus is connected to the heating device for supplying heat to maintain the temperature in the primary oxidizer above 85 ℃. The method according to claim 6, Dietary sulfur production apparatus is connected to the oxygen exhaust pipe for discharging the oxygen generated by the oxidation reaction in the primary oxidizer. The method according to claim 6, Dietary sulfur production apparatus for installing a filtration device in the transfer line to remove foreign matter contained in the intermediate product supplied from the primary oxidizer to the secondary oxidizer. The method according to claim 7, The secondary oxidizer is provided with an ozone exhaust device for discharging excess ozone that does not participate in the reaction in the ozone supplied from the ozone supply device, The ozone exhaust device is connected to the ozone concentration measuring device for measuring the concentration of ozone is exhausted, The secondary oxidizer is connected to the cooling device for supplying cooling water for cooling, Dietary sulfur production apparatus is connected to the secondary oxidizer is a cooling water discharge device for discharging the supplied cooling water. The method according to claim 10, The control device for inputting the ozone concentration measuring device installed in the ozone exhaust device, the signal from the pH correction device, the operating condition setting value of each device, and the control signal of the heating device, pH correction device, ozone supply device is outputted Dietary sulfur manufacturing apparatus further included.

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