KR101037512B1 - System and Method for Hydrogen-Rich Gas Production from By-Product Glycerol of Biodiesel Production - Google Patents

Abstract

The present invention relates to a system and method for producing high concentration hydrogen using waste glycerol, and more particularly, to produce a synthesis gas containing high concentration hydrogen by gasifying the waste glycerol generated as a by-product in the biodiesel production process in a supercritical water. It relates to a hydrogen production system and a hydrogen production method.

The present invention is to prepare a dilution by mixing the waste glycerol in the oil phase with the treated water, gasification of it in supercritical water to treat the organic material in the diluent, and receiving a flammable synthesis gas containing hydrogen in the organic material treatment process By simplifying the equipment and methods, high-efficiency, high-concentration hydrogen is produced at low cost, thereby improving the industrial use value.

Biodiesel, Waste Glycerol, Supercritical Water, Gasification, High Concentration

Description

System and Method for Hydrogen-Rich Gas Production from By-Product Glycerol of Biodiesel Production}

The present invention relates to a system and method for producing high concentration hydrogen using waste glycerol, and more particularly, to produce a synthesis gas containing high concentration hydrogen by gasifying the waste glycerol generated as a by-product in the biodiesel production process in a supercritical water. It relates to a hydrogen production system and a hydrogen production method.

In the 21st century, fossil fuel consumption is increasing year by year due to the emergence of large emerging industrial countries such as China and India and the continuous expansion of the global economy. Carbon dioxide generated from the use of fossil fuels is a major greenhouse gas and is known to have a significant impact on global warming. Annual CO2 emissions from domestic fossil fuel use are among the top 10 in the world, which is higher than the economic scale. Therefore, for the sustainable growth of humankind, it is urgent to develop and use renewable energy.

Biodiesel is a renewable energy produced through the transesterification of vegetable or animal fatty acids and alcohols, and is mainly developed and used as a substitute fuel for diesel fuel, which is a transportation fuel. Biodiesel has a significant increase in domestic production year by year because of the advantages that the manufacturing process is simpler than other liquid renewable fuels and can be mixed with existing diesel fuels.

In biodiesel production, waste glycerol is generated as a by-product, which accounts for about 10% of biodiesel production. Glycerol is an important substance used in various industries such as food, pharmaceuticals and chemistry. However, waste glycerol, a by-product of biodiesel production, contains glycerol in addition to unreacted fatty acids, alcohols and biodiesel, and salts such as calcium hydroxide (KOH) used as a catalyst. Therefore, if you want to use glycerol contained in the waste glycerol requires a complicated separation and purification process (Korean Utility Model 20-2008-0003102). Meanwhile, as the production of biodiesel increases rapidly, the amount of waste glycerol is increasing proportionally, while the demand for waste glycerol as an industrial raw material is not increasing. Accordingly, in Europe where the biodiesel industry is mature, waste glycerol is approached as a waste treatment concept rather than an industrial raw material.

Nevertheless, various techniques related to the recycling of waste glycerol have been developed. Korean Patent No. 10-0870370 and Korean Patent No. 10-0870369 describe a method for producing propanediol using waste glycerol, and Korean Patent No. 10-0800210 discloses glycemia resulting from the conversion of animal fat in biodiesel production. A method for preparing dichloropropanol in cerol has been reported. Korean Patent No. 10-0456450 describes a biological method for converting waste glycerol to 1,3-propanediol. However, the existing waste glycerol recycling method as described above is a method of producing a high value-added chemical raw material from glycerol, so only part of the waste glycerol component can be used to avoid the generation of process waste again.

On the other hand, Korean Patent No. 10-0916210 and Korean Patent No. 10-0780910 report a hydrogen production system and method by supercritical water vaporization of an aqueous phase organic material. However, the above methods are limited to water-soluble organic substances, and there is a technical difficulty in applying them as an energy recovery method of waste glycerol in an oil phase.

The high concentration hydrogen production system and hydrogen production method using waste glycerol as a byproduct in the biodiesel production process according to the present invention,

Waste glycerol of complex nature is mixed with water without separating and refining process and gasified in supercritical water to treat more than 99% organic matter, and in the process, it produces flammable synthesis gas containing more than 50 mol% hydrogen. It is an object of the present invention to provide a hydrogen production system and a hydrogen production method for treating waste glycerol, a by-product of diesel processing, and generating energy therefrom.

High concentration hydrogen production system using waste glycerol as a byproduct in the biodiesel production process of the present invention for solving the above problems,

In a system for gasifying waste glycerol generated as a by-product during biodiesel production and producing high concentration hydrogen therefrom, a waste glycerol stock reservoir for storing the waste glycerol stock produced in the biodiesel production process, and the waste glycerol stock solution A treatment water storage tank for dilution, a valve and a flow controller installed in the waste glycerol stock solution and the treatment water storage tank, respectively, to control discharge, and a diluent storage tank for mixing and storing the waste glycerol stock solution and the treated water at a predetermined ratio; A reaction input device including a high pressure pump to supply the stored waste glycerol diluent at a constant pressure and a flow rate; A preheating tube for transferring the diluent supplied to the high pressure pump, an internal heater installed inside the preheating tube, a cross provided at each of the inlet and the outlet of the preheating tube for introducing and discharging the diluent into the preheating tube; Preheating including a heating furnace containing a preheating tube, a coil-type heater installed on the outer wall of both ends of the preheating tube between the preheating tube and the heating furnace, and a high temperature filter installed at the outlet of the preheating tube that may be generated during the preheating process. An apparatus; A reaction tube in which the preheated waste glycerol diluent is introduced to generate a product by a supercritical water gasification reaction, and a cross which is respectively installed at the inlet and the outlet of the reaction tube to stably inlet the preheated diluent into the reaction tube and discharge the reactant; A coil heater installed on the outer wall of the inlet side end portion of the reaction tube between the reaction tube and the heating furnace, and installed at the discharge side end of the reaction tube to cool the reaction product. A supercritical water gasification reaction apparatus including an indirect heat exchanger configured to be installed at the end of the reaction tube and supporting the catalyst bed support to prevent the catalyst charged in the reaction tube from being discharged; A gas-liquid separator which removes the solid material contained in the product cooled by the heat exchanger using a room temperature filter, and discharges the product to a gas pressure and a liquid phase by decompressing the product at atmospheric pressure with a post pressure controller; A product gas storage tank for collecting and storing a product gas containing a high concentration of hydrogen, which is a gaseous product separated by the gas-liquid separator; It is configured to include; a circulating pipe for transferring the treated water, which is a liquid product separated from the gas-liquid separator, to the treated water storage tank by pumping to be used for diluting the waste glycerol stock solution.

In addition, a high concentration hydrogen production method using waste glycerol as a byproduct in the biodiesel production process according to the present invention,

Supercritical gasification of waste glycerol using the hydrogen production system of claim 1 comprising a reactant input device, a preheating device, a supercritical water gasification reaction device, a gas-liquid separator, a product gas storage tank, and a return tube In the method of producing hydrogen, the valve under the treated water storage tank is opened, and water is introduced into the waste glycerol diluent storage tank using a pump, which is introduced into all lines including a preheating tube and a reaction tube using a high pressure pump. A water inflow step; Increasing the pressure of the water flowing in all the lines between the high pressure pump and the after pressure controller to the reaction pressure by using the after pressure controller after confirming that the introduced water comes out to the gas-liquid separator; After the pressure reaches the reaction pressure and it is confirmed that there is no leakage, open the valve at the bottom of the waste glycerol stock reservoir, and flow the waste glycerol stock into the diluent storage tank with a pump. Preparing diluent waste glycerol to be diluted; Putting the waste glycerol diluent into a preheating tube through a high pressure pump, and heating the injected diluent with a heater to preheat it to a constant temperature; Flowing the preheated diluent into the reaction tube and heating it to a reaction temperature to perform supercritical water gasification reaction; The product produced by the reaction is quenched to room temperature by an indirect heat exchanger, the solids are removed by a room temperature filter, and then depressurized to atmospheric pressure through a post pressure controller, and the reduced product is subjected to a gaseous product and a liquid phase through a gas-liquid separator. Separating the product, and storing the high concentration hydrogen, the gaseous product, into the generated gas storage tank, and storing the treated gas, which is a liquid product, by pumping the pump and returning it to the treated water storage tank through a return pipe. It is done by

High concentration hydrogen production system and hydrogen production method using waste glycerol as a by-product in the biodiesel production process according to the present invention,

A diluent is prepared by mixing waste glycerol, which is an oil phase, with a treated water, and gasifying it in supercritical water to treat organic substances in the diluent, and receiving flammable synthetic gas containing hydrogen during the organic substance treatment. By simplifying the method, high-efficiency, high-concentration hydrogen is produced at low cost, thereby improving the industrial use value.

Hereinafter, a high concentration hydrogen production system and a hydrogen production method using waste glycerol as a by-product in the biodiesel production process according to the present invention will be described in detail with the accompanying drawings.

1 is a schematic diagram showing a high concentration hydrogen production system using waste glycerol according to the present invention, Figure 2 is a block diagram showing a high concentration hydrogen production method using waste glycerol according to the present invention.

As shown, the high concentration hydrogen production system 10 according to the present invention includes a reactant input device 20, a preheater 30, a supercritical water gasification reaction device 40, a gas-liquid separator 50, and a production gas. It consists of a reservoir 60 and a flow tube 70.

The reactant input device 20 includes: a waste glycerol stock solution storage tank 21 for storing waste glycerol generated during biodiesel production; A treated water storage tank 22 for storing the treated water discharged from the gas-liquid separator 50 and replenishing the insufficient amount from the outside; A diluent storage tank 23 for mixing the waste glycerol stock with water, which is treated water, in a constant ratio to produce and store a uniform dilution solution; It is composed of a high-pressure pump 26 to continuously input the prepared diluent to the preheating tube at a high pressure reaction pressure.

The preheating device 30 includes a preheating tube 31 for preheating the added diluent to a constant temperature; One or more preheater internal heaters 32; Two coil heaters 35a and 35b provided on the outer wall of the preheating tube; One or more heating furnaces (34) installed to contain a preheating tube; One thermocouple (T) installed to measure the temperature inside the preheating tube; At least one high temperature filter 36 installed at an outlet of the preheating tube to remove solid substances which may occur during the preheating process; It consists of crosses 33a and 33b respectively provided at the front and rear ends of the preheating tube.

In addition, the supercritical water gasification reaction device 40 includes a supercritical water gasification reaction tube 41 for gasifying the preheated diluent; One or more coil heaters 44 installed on the outer wall of the front end of the reaction tube to supply heat for the reaction; At least one heating furnace 43 installed outside the reaction tube; Two or more thermocouples (T) for measuring the reaction tube shear temperature and the internal temperature; An indirect heat exchanger (45) for cooling the product produced by the reaction; One catalyst bed support 46 for preventing the solid catalyst charged into the reaction tube from being discharged; And crosses 42a and 42b provided at the front and rear ends of the reaction tube.

The gas-liquid separator 50 is composed of one or more, and removes the solid material that may occur in the gasification reaction process with one or more room temperature filter 51, and the high-pressure pump through one or more after-pressure controller 52 This is a device for controlling the pressure inside all the flow tubes, the preheating tubes 31, and the reaction tubes 41 between the 26 and the gas-liquid separator 50 to separate the products at room temperature and atmospheric pressure into gas and liquid phase. .

The product gas storage tank 60 collects and stores high velocity hydrogen, which is a separated gaseous product, more specifically, the product gas including the hydrogen by measuring the flow rate by a gas flow meter 61, and then, or It consists of a plurality.

In addition, the flow pipe 70 is pumped to the treated water of the liquid separated in the gas-liquid separator 50 is transferred to the treated water storage tank 22 to be used as dilution water of the waste glycerol stock solution. Here, when the amount of the treated water used for the dilution is insufficient, to replenish the water of good quality from the outside.

On the other hand, the preheating tube 31 can be used as a reaction tube by heating the heating temperature to the reaction temperature. Therefore, the preheating tube and the reaction tube may be used as one tube and the tube may be divided into a preheating zone and a reaction zone.

In addition, the reaction tube 41 may be used to fill the solid catalyst in order to increase the gasification rate, the filling catalyst may be used to fill the reaction tube without flow, or to make the flow.

High concentration hydrogen production method using waste glycerol according to the present invention,

Including a reactant input device 20, preheater 30, supercritical water gasification reaction device 40, gas-liquid separator 50, product gas storage tank 60, the circulating pipe 70 In the method for producing high concentration hydrogen by supercritical water gasification of waste glycerol using the configured hydrogen production system 10,

Line water inflow step S1 is performed in advance. In the step, the valve 24a at the bottom of the waste glycerol stock solution 21 is closed, and only the valve 24b at the bottom of the treatment water storage 22 is opened to flow the stored water into the diluent storage tank 23, which is continuously high pressure. It is a step of introducing into the preheating tube 31 by using the pump 26.

Next, the pressure rising step S2 is performed. The step is to increase the flow pressure of all the pipes to the reaction pressure by using the after-pressure controller 52 when it is confirmed that the injected water is discharged to the gas-liquid separator 50 through the reaction tube (41). In addition, when water is discharged to the gas-liquid separator 50 at the reaction pressure and no water leaks from all the lines, water is supplied using the heating furnace 34 and the coil heaters 35a and 35b of the preheating tube 31. The water is heated to the preheating temperature and then the water is heated to the reaction temperature using a heating furnace 43, a coil heater 44, or the like provided in the reaction tube 41.

When the pressure is raised to the reaction pressure to prepare a waste glycerol dilution (S3) is carried out. In this step, the valve 24a at the bottom of the waste glycerol stock solution 21 is opened, and the waste glycerol stock solution is introduced into the diluent stock tank 23. At this time, by using the flow rate controller (25a, 25b) installed in the bottom of the stock solution storage tank 21 and the treated water storage tank 22 to control the flow rate of the waste glycerol stock solution and the water treated water to the desired dilution ratio.

In addition, in the diluent storage tank 23, the waste glycerol stock solution and water introduced using a stirrer are uniformly mixed to prepare a diluent which is a reactant.

Next, the pre-heated waste glycerol dilution step (S4) and the supercritical water gasification reaction step (S5) is performed with the preheated diluent.

The prepared diluent is added to the preheating tube 31 through the high pressure pump 26 to be preheated to the reaction temperature, and the supercritical water gasification reaction is performed in the reaction tube 41.

When the reaction is completed, the product gas storage and treatment water recycling step (S6) is performed. Since the product generated by the supercritical water gasification reaction may include solids, the solids are removed through the room temperature filter 51, and the high concentration hydrogen is introduced into the gas-liquid separator 50 through the after pressure controller 52. Separated into generated gas and treated water. The generated gas is measured by measuring the flow rate of the flow through the flow meter 61 and stored in the generated gas storage tank (60). In addition, the separated treated water is pumped and supplied to the treated water storage tank 22 installed at the front end of the apparatus for dilution of the waste glycerol stock through the return pipe 70 for reuse.

Referring to the hydrogen production or operation method using the above device, in the present invention, the supercritical water gasification reaction device 40 may be used to charge the catalyst after mounting the catalyst bed support 46 in the lower portion. Even when it is not necessary to charge the catalyst, the catalyst bed support 46 can be used in a mounted state.

When the catalyst is charged and the assembly and preparation of all the apparatuses including the reactor 40 are completed, the water being stored in the treated water storage tank 22 is opened and the valve 24b at the bottom thereof is introduced into the waste glycerol diluent storage tank 23. This is sent to all lines of the reaction apparatus, including the preheating tube 31 and the reaction tube 41 by using the high pressure pump 26. At this time, the valve 24a installed at the bottom of the waste glycerol stock solution 21 is kept locked.

When it is confirmed that the water flowing into the reactor comes out of the gas-liquid separator 50, the pressure of the reactor is increased from the normal pressure to the pressure of 23 MPa or more using the back pressure controller 52.

Check the leakage of all parts of the reactor and in the absence of leaks, the preheater tube inner heater 32, preheater outer wall coil type heaters 35a, 35b, and the heating furnace 34 are operated in sequence to preheat the tube. 31) Increase the internal temperature to about 400 ℃. The internal temperature of the preheating tube 31 is measured using a thermocouple (T).

Next, the outer tube coil heater 44 and the heating furnace 43 are operated to heat the reaction tube 41 so that the internal temperature of the supercritical water gasification reaction tube 41 is at least 500 ° C or higher. At this time, the temperature inside the reaction tube 41 is measured using a thermocouple (T).

When the reaction pressure and the reaction temperature are maintained at 23 MPa or more and about 600 ° C, respectively, the valve 24a installed at the bottom of the waste glycerol stock solution 21 is opened, and the waste glycerol stock solution is introduced into the waste glycerol diluent stock 23. At this time, in order to obtain a constant dilution ratio and flow rate, the flow controllers 25a and 25b are used to control the flow rate of the waste glycerol stock solution and the treated water.

In the waste glycerol dilution tank, the waste glycerol stock solution and water introduced by using a stirring device are mixed to be in a uniform phase.

The mixed diluent is preheated to about 400 ° C. while passing through the preheating tube 31 by using the high pressure pump 26 through the preheating tube 31 from the outlet installed at the bottom of the waste glycerol diluent storage tank and passing the preheating tube 31. It is heated to the reaction temperature while passing (41).

The reaction temperature will be determined depending on the organic material concentration and the input flow rate of the waste glycerol diluent as a reactant, but it is preferable to operate in the range of 500-700 ℃. The reaction product is cooled to 50 ° C. or less while passing through an indirect heat exchanger (45) installed at the end of the furnace (41), and the solid material is removed while passing through a room temperature filter (51). While passing through (52), the reaction pressure is reduced to normal pressure.

The product at room temperature and atmospheric pressure flows into the gas-liquid separator 50 and is separated into gas phase and liquid phase products, respectively. The gaseous product is measured using the gas flow meter 61 and then flowed into the product gas storage tank 60 to be temporarily stored. If necessary, a gas booster or the like can be used to store the generated gas.

The liquid product is collected at the bottom of the gas-liquid separator and then recycled to the treatment water storage tank 22 through a pump. If the treated water is insufficient, replenish high quality water such as tap water.

Hereinafter, an example of supercritical water gasification using a reactant (diluent) made by diluting the waste glycerol stock solution generated in the biodiesel production process by the system and method according to the present invention was described.

Example 1: Effect of Catalyst and Reaction Temperature

-Reaction temperature for removal of product gas and organic matter during supercritical water gasification of 27.6MPa, 11 h ^-1 LHSV operating conditions by reacting 10 times diluting waste glycerol stock in a continuous flow tubular reactor without solid catalyst The influence is shown in the following [Table 1].

 In this patent, LHSV is defined as the reactant input flow rate divided by the reactor volume at room temperature.

The main materials of the gas produced at all reaction temperatures were hydrogen, carbon monoxide, carbon dioxide, methane and ethane, and trace amounts of ethylene, propylene and propane gas were detected at reaction temperatures below 580 ° C.

In general, the gas production rate (hourly gas production divided by the reactor volume) did not change significantly in the reaction temperature range of 600-720 ° C., but the composition of the product gas was slightly changed.

Hydrogen showed higher mole fraction at lower reaction temperature, while carbon monoxide, methane and methane showed lower molar fraction at higher reaction temperature.

This tendency is different from the effect of reaction temperature on the product gas composition obtained from supercritical water gasification of cellulose systems such as glucose. In the case of glucose, the fraction of hydrogen in the product gas increased with increasing reaction temperature, and the contents of carbon monoxide and lower hydrocarbons decreased.

In addition, at the initial concentration of similar reactants, the hydrogen content in the gas produced by supercritical water gasification of waste glycerol was significantly higher than that of supercritical water gasification of glucose because calcium hydroxide (KOH) present in the waste glycerol acted as a gasification catalyst. .

Calcium hydroxide is used as a catalyst in the reaction to produce biodiesel from fatty acids. Despite the presence of acidic substances such as unreacted fatty acids in the waste glycerol, the pH was about 10 because the large amount of calcium hydroxide used as a catalyst for biodiesel production.

According to the literature, calcium hydroxide also acts as a catalyst in the supercritical water gasification of organic materials. The organic substance concentration in the waste glycerol dilution was represented by chemical oxygen demand, that is, COD. The COD removal rate was very high at around 99% at the reaction temperature of 610 ℃ and higher, and colorless and transparent treated water was obtained. The gasification rate was drastically lowered and a white opaque treated water was obtained. In addition, the gas production rate was also sharply reduced at the reaction temperature of 580 ℃.

-The reaction temperature effect on the supercritical water gasification of the waste glycerol dilution in the activated charcoal packed bed is shown in FIG.

As shown in [Table 2], the activated charcoal was charged to the tubular reactor and the supercritical gasification of waste glycerol was carried out under 27.6MPa, 11 h ^-1 LHSV operating condition. The COD removal rate of the treated water was also maintained at about 99%.

However, there was no significant change in the composition of the product gas and the mole fraction with temperature at each temperature.

As a result, activated charcoal was found to be an effective catalyst for the total gas production by the supercritical water gasification of waste glycerol and the removal of organic matter from the treated water.

-The reaction temperature effect on the supercritical water gasification of the waste glycerol dilution in the Ni-Y / AC packed bed is shown in FIG.

[Table 3] is an example of the supercritical gasification experiment of waste glycerol in a tubular reactor with Ni-Y / AC catalyst and 27.6 MPa, 11 h ^-1 LHSV.

In general, the reaction temperature effect on the waste glycerol gasification was similar to the results in the activated charcoal packed bed, but the gas production rate was decreased at the reaction temperature above 700 ℃. This can be interpreted as part of the generated hydrogen was consumed in methane production as the methanation reaction was activated at high temperature, as can be seen in the product gas composition.

According to the Korean patent (Registration No. 10-0916210), Ni-Y / AC has high activity and stability in the hydrogen production reaction by supercritical water gasification of glucose or cellulose-based water-soluble organic substances.

However, in the case of waste glycerol, the hydrogen mole fraction in the produced gas was not significantly higher than the results of the non-catalytic experiment shown in [Table 1] or the activated charcoal shown in [Table 2]. The hydrogen fraction was rather low.

From these results, it can be said that in the case of the waste glycerol containing calcium hydroxide, the calcium hydroxide in the dissolved state has higher catalytic activity for gasification than the solid Ni-Y / AC catalyst.

However, in recent biodiesel production processes, the use of salts such as calcium hydroxide as a catalyst is avoided, and solid catalysts such as zeolites have been developed and utilized. Therefore, since calcium hydroxide does not exist in the waste glycerol generated in the process, Ni-Y / AC may play a large role as a supercritical water gasification catalyst in this case.

In fact, the results of supercritical water gasification experiments on glycerol, the main component of waste glycerol, showed that the hydrogen content in the gas produced by the non-catalyzed gasification of 1.2 mol / L glycerol at 650 ° C was only about 40 mol%. Under the same conditions, the Ni-Y / AC catalytic gasification resulted in a hydrogen content of 55 mol%, similar to the waste glycerol results in Table 3.

Therefore, it is believed that Ni-Y / AC may be usefully used as a catalyst for supercritical water gasification of waste glycerol containing no salt such as calcium hydroxide.

Example 2 Effect of Initial Concentration of Waste Glycerol

The effect of the initial concentration of waste glycerol on the supercritical water gasification at 650 ℃, 27.6MPa, 11 h ^-1 LHSV operating conditions in the Ni-Y / AC packed bed was investigated.

As the initial concentration of waste glycerol increases, the hydrogen content of the generated gas tends to decrease and the methane content tends to increase.The rate of gas generation increases, but the rate of gas generation compared to the injected organic material (gas generation rate divided by the initial concentration of waste glycerol). Decreased significantly.

While the initial concentration of waste glycerol increased threefold, the COD removal rate of treated water did not change significantly, but the color changed from colorless to opaque white. In general, it can be concluded that the initial concentration of reactants in the treatment by supercritical water gasification of waste glycerol greatly influences the gasification results.

Example 3 Influence of Reagent Mass Flow Rate

Table 5 shows the effects on the product gas and the treated water of the glycerol diluent input flow rate for supercritical water gasification at 650 ° C and 27.6MPa operating conditions in a packed bed of Ni-Y / AC catalyst.

Hydrogen content in the product gas tended to increase slightly as the input flow rate increased. Methane and ethane decreased, but the gas production rate increased in direct proportion to the input flow rate.

The COD removal rate of the treated water was almost unchanged, but the input flow rate was slightly white at 33h ^-1 LHSV.

Therefore, it can be concluded that the input flow rate within the experimental range does not significantly affect the supercritical gasification treatment of waste glycerol.

1 is a process chart showing a high concentration hydrogen production system using waste glycerol according to the present invention.

Figure 2 is a block diagram showing a high concentration hydrogen production method using waste glycerol according to the present invention.

<Description of the symbols for the main parts of the drawings>

10: hydrogen production system

20: reactant injection device

21: waste glycerol stock solution 22: treated water storage tank

23: diluent reservoir 24a, 24b: valve

25a, 25b: flow controller 26: high pressure pump

30: preheating device

31: preheater tube 32: internal heater

33a, 33b, 42a, 42b: cross 34, 44: heating furnace

35a, 35b, 44: coil heater 36: high temperature filter

40: supercritical water gasification reactor

41: reaction tube 45: indirect heat exchanger

46 catalyst bed support

50: gas-liquid separator

51: room temperature filter 52: after pressure controller

60: product gas storage tank

61: gas flow meter

70: flow hall

Claims (5)

In the system for gasifying and treating waste glycerol generated as a by-product during biodiesel production, and producing high concentration hydrogen therefrom, Waste glycerol stock solution storage tank 21 for storing the waste glycerol stock solution generated in the biodiesel production process, a treated water storage tank 22 for diluting the waste glycerol stock solution, the waste glycerol stock solution 21 and the treated water storage tank ( 22 and valves 24a and 24b and flow controllers 25a and 25b, respectively, installed in each of the outlets, and a diluent storage tank 23 for mixing and storing the waste glycerol stock solution and the treated water at a predetermined ratio. A reactant input device 20 including a high pressure pump 26 for supplying the waste glycerol diluent at a constant pressure and flow rate; A preheating tube 31 for transferring the diluent supplied to the high pressure pump, an internal heater 32 installed inside the preheating tube, and an inlet and an outlet of the preheating tube, respectively, for diluting the liquid into the preheating tube; Crosses 33a and 33b to be discharged, a heating furnace 34 including the preheating tube, a coil heater 35a and 35b provided at outer walls of both ends of the preheating tube between the preheating tube and the heating furnace, A preheating device 30 including a high temperature filter 36 installed at a preheating tube outlet which may be generated during a preheating process; The preheated waste glycerol diluent is introduced into the reaction tube 41 to produce a product by the supercritical water gasification reaction, and the preheated diluent is respectively installed at the inlet and the outlet of the reaction tube to stably inlet and discharge the reactant. A cross section (42a, 42b), a heating furnace (43) installed to contain the reaction tube, and a coil heater (44) provided on the outer wall of the inlet end portion of the reaction tube between the reaction tube and the heating furnace; And an indirect heat exchanger (45) installed at the discharge side end of the reaction tube to cool the reaction product, and a catalyst bed support (46) installed at the reaction tube discharge end to support the catalyst charged in the reaction tube from being discharged. Supercritical water gasification reaction device 40 including; The gas-liquid separator which removes the solid material contained in the product cooled by the heat exchange with a room temperature filter 51, and the discharged product is decompressed to a normal pressure state by a post pressure controller 52 to separate the product into a gas phase and a liquid phase. 50); A product gas storage tank 60 for collecting and storing a product gas containing high concentration of hydrogen, which is a gaseous product separated by the gas-liquid separator; High-density hydrogen production using waste glycerol, characterized in that it comprises a; circulating pipe (70) for transferring the treated water, which is a liquid separated in the gas-liquid separator to the treated water storage tank by pumping to be used for diluting the waste glycerol stock solution. system. Supercritical gasification of waste glycerol using the hydrogen production system of claim 1 comprising a reactant input device, a preheating device, a supercritical water gasification reaction device, a gas-liquid separator, a product gas storage tank, and a return tube In the method of producing hydrogen, A water inflow step (S1) of opening a valve under the treated water storage tank, introducing water into a waste glycerol diluent storage tank using a pump, and introducing the same into all lines including a preheating tube and a reaction tube using a high pressure pump; Increasing the pressure of the water flowing in all the lines between the high pressure pump and the after pressure controller to the reaction pressure by using the after pressure controller after confirming that the introduced water comes out to the gas-liquid separator (S2); After the pressure reaches the reaction pressure and it is confirmed that there is no leakage, open the valve at the bottom of the waste glycerol stock reservoir, and flow the waste glycerol stock into the diluent storage tank with a pump. Preparing diluent waste glycerol to be diluted (S3); Putting the waste glycerol diluent into a preheating tube through a high pressure pump, and heating the injected diluent with a heater to preheat it to a predetermined temperature (S4); Introducing the preheated diluent into a reaction tube and heating it to a reaction temperature to perform a supercritical water gasification reaction (S5); The product produced by the reaction is quenched to room temperature by an indirect heat exchanger, the solids are removed by a room temperature filter, and then depressurized to atmospheric pressure through a post pressure controller, and the reduced product is subjected to a gaseous product and a liquid phase through a gas-liquid separator. Separating the product, the high concentration hydrogen of the gaseous product is stored in the product gas storage tank, and the treated water is a liquid product pumped by a pump and returned to the treated water storage tank through the return pipe to the treated water storage step (S6) High concentration hydrogen production method using waste glycerol, characterized in that consisting of. The method of claim 2, The waste glycerol dilution solution is a high concentration hydrogen production method using waste glycerol, characterized in that diluted with water so that the organic substance concentration is 5,000 to 500,000 mgO ₂ / L on the basis of chemical oxygen demand (COD). The method of claim 2, The preheating tube (31) inside the high concentration hydrogen production method using waste glycerol, characterized in that maintained at a pressure of 23 ~ 40MPa and a temperature of 350 ~ 450 ℃. The method of claim 2, The reaction tube (41) inside the high concentration hydrogen production method using waste glycerol, characterized in that maintained at a pressure of 23 to 40MPa, the temperature of 500 to 750 ℃.

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