KR101381301B1 - Reactor System for Bio-Oil Supercritical Water Reforming with Vertical Type Reactor and Operation Method of Thereof - Google Patents

Abstract

The present invention relates to a biooil supercritical water reforming reaction system having a vertical reactor for producing flammable syngas by continuously reforming biooil, which is a pyrolysis oil obtained by rapid pyrolysis of a solid wood-based biomass such as wood, in a supercritical water and its operation. It is about a method.
The reaction system of the present invention includes a reactant input device for inputting a reactant mixed with biooil and water received from woody biomass; A vertical reactor for preheating the introduced reactant and reforming the preheated reactant under supercritical water to produce a product containing combustible syngas; And a post-treatment apparatus for cooling the product produced in the vertical reactor and phase-separating to produce a synthesis gas from which foreign substances have been removed.

Description

Reactor System for Bio-Oil Supercritical Water Reforming with Vertical Type Reactor and Operation Method of Thereof}

The present invention relates to a biooil supercritical water reforming reaction system having a vertical reactor for producing flammable syngas by continuously reforming biooil, which is a pyrolysis oil obtained by rapid pyrolysis of a solid wood-based biomass such as wood, in a supercritical water and its operation. It is about a method.

Biomass is attracting worldwide attention as an alternative energy source for fossil fuels as a renewable resource. Wood-based biomass, especially wood, such as second-generation biomass, is a non-edible resource that is free from social conflicts stemming from the use of food and can contribute to solving the energy and environmental problems of humankind by abundant global reserves.

Typical energy utilization technologies of conventional commercialized woody biomass include combustion and gasification. Combustion is a well-known technique from the past and is a method of obtaining thermal energy through high-temperature oxidation reaction in oxygen or air. Thermal energy can be converted to water vapor and hot water, which is also used for electricity production using steam turbines. Generally, the biomass gasification technology is a partial oxidation gasification, and is a method of producing flammable syngas by directly liquefying organic components in raw materials by injecting woody biomass as raw material into a gasification reactor maintained at a high temperature. Direct gasification technologies of biomass have been developed in various forms according to reactor type, gasification reaction method, etc. However, the composition of the process is very similar to the synthesis gas production technology by direct gasification of coal.

BACKGROUND ART [0002] Energy production technology from woody biomass such as conventional combustion or gasification has at least two problems. First, since both technologies are operated by large-scale facilities, there must be an area with abundance of resources capable of supplying more than several hundred tons of biomass per day in a stable manner. Woody biomass is low in energy density and scattered in the area of origin, resulting in high transportation costs. The second problem is that various separation and purification devices are needed to separate the dust or tar generated from the combustion or gasification process from the product. Particularly, in the case of gasification technology, a complex type of gasification reactor (Korean Patent Registration No. 10-0784851, Korean Patent Registration No. 10-069508) or a tar removal device (Korea Patent Registration No. 10-0819505, Patent Registration No. 10-0896933) is additionally attached. Since the direct gasification technology of the woody biomass is composed of various unit processes from the preparation of the raw material to the purification process of the synthesized gas produced, it is generally inevitable to enlarge the facility in order to meet the economical efficiency. However, forest biomass, the main woody biomass in Korea, is scattered because the amount is not constant every year, and the energy content per unit volume is very low as most are small-size materials. This leads to high raw material transportation costs, which is a major reason for lowering the economics of the centralized large gasification process.

Therefore, a recently developed technology is a rapid pyrolysis technique in consideration of the low energy density of such woody biomass. This technology is a technology to convert woody biomass composed of polymers such as cellulose, hemicellulose, and re-greens into exothermic materials by externally heating. It has advantages such that reaction temperature is lower than combustion or gasification and it operates at normal pressure. The main product is bio-oil, which is a liquid-phase pyrolysis product. As a by-product, carbide (bio-char) and flammable syngas are produced. The rapid pyrolysis apparatus is relatively simple and can be manufactured as a portable type. Since bio oil has 4 times higher energy density than liquid wood biomass and is liquid, it can greatly reduce transportation and storage costs. Therefore, the cost of raw material is transferred by producing and demanding bio oil using mobile pyrolysis device in the place where biomass raw materials are located. (D. Mohan et al., Energy & Fuels 2006, 20, 848-889). Bio-oil can be used for various purposes. In particular, synthetic gas can be produced by reforming and then applied to a gas engine or gas turbine for use in electricity production. In this way, a ligneous biomass is firstly rapidly pyrolyzed and converted into bio oil, which is secondarily reformed to produce indirect energy for biomass production (Korean Patent Registration No. 10-1137897). However, in order to produce syngas by modifying bio-oil, specific reaction equipment and operating method are needed. A method of applying conventional steam reforming of methane or naphtha by a bio-oil reforming method may be considered. However, when applied to a mixture of organic materials having various molecular weights and physical properties such as bio-oil, the steam reforming process causes a side reaction in addition to the objective reaction, resulting in a decrease in the yield of synthesis gas, There is a disadvantage that the same impurities are generated and it is inevitable to introduce a follow-up device to remove the impurities.

The biooil supercritical water reforming reaction system having a vertical reactor of the present invention and its operation method are

Reaction system having a vertical reactor for continuously producing high quality combustible synthesis gas free of impurities such as tar or char by reforming bio-oil obtained by rapid pyrolysis of wood-based biomass in supercritical water And to provide an optimal operation method thereof.

Biooil supercritical water reforming reaction system having a vertical reactor of the present invention for solving the above problems,

A reactant input device for inputting a reactant mixed with biooil and water received from woody biomass; A vertical reactor for preheating the introduced reactant and reforming the preheated reactant under supercritical water to produce a product containing combustible syngas; And a post-treatment apparatus for cooling the product produced in the vertical reactor and phase-separating to produce a synthesis gas from which foreign substances have been removed.

The vertical reactor, a vertical cylinder is formed in the middle of the catalyst support which is a step protruding toward the central axis along the inner circumferential surface, and the inside of the catalyst support is divided into an upper reaction chamber and a lower preheating chamber by placing a metal mesh, A vertical reactor for communicating with a reactant supply pipe at a lower side of the preheating chamber and a discharge pipe at a top of the reaction chamber for discharging a product; An internal heater disposed in the preheating chamber to heat a reactant; An external heater installed on the outer wall of the preheat chamber in the form of a coil to heat the reactant introduced; A thermocouple disposed in the preheating chamber and the reaction chamber to measure a preheating temperature and a reaction temperature of a reactant; A solids storage tank communicating with the bottom of the vertical reactor and storing a solid which is generated as a side reaction (coking) while the reactant is heated and settles; A catalyst layer filling the upper portion of the metal mesh of the reaction chamber; A disc filter installed on the catalyst layer to prevent the outflow of the catalyst by floating; It is configured to include; a heating furnace which is installed to contain a vertical reactor to heat the vertical reactor.

In addition, the operating method of the biooil supercritical water reforming reaction system having a vertical reactor of the present invention,

The organic material concentration of the reactant prepared by diluting the biooil and water is about 50,000 to 200,000 mgO ₂ / L based on COD, and the preheating chamber of the vertical reactor is 500 to 650 ° C. and the reaction chamber is It is characterized in that it is operated by supplying the reactants at a reaction temperature in the range of 650-710 ℃, reaction pressure in the range of 25-35 MPa, inflow rate of 25-50 h-1 LHSV.

As described in detail above, a biooil supercritical water reforming reaction system having a vertical reactor of the present invention and a method of operating the same,

Since it is possible to continuously produce a clean flammable synthesis gas free from impurities such as tar from bio oil, various separation and purification processes for removing impurities in the product gas may be omitted in steam reforming of conventional biooil.

In addition, the reactor is formed integrally with a preheating function in the inlet portion, so that the reactant flows from the inlet portion, which is the lower part of the reactor, to the upper part, so that the rapid preheating and reforming reactions are performed. (char) was collected at the bottom of the reactor by gravity. This separation of the car has an effect that the production of gas by the reforming reaction can be stably caused by blocking the inflow of tea in the reaction process using the catalyst of the reactor. That is, it is possible to prevent the phenomenon that the catalytic activity is lowered by the solid material is fixed on the surface of the catalyst filled in the reactor during the reforming reaction can perform a more stable and effective catalytic reaction.

In addition, the reactor of the present invention separates the reaction tube in which the reforming reaction takes place and the preheating tube for preheating the reactants, and interconnects the reaction tube and the preheating tube with a union or reducer to protrude the inner side of the connecting portion. Part of the catalyst layer support (support), and the catalyst layer support on the upper part by mounting a metal mesh having holes (holes) narrower than the catalyst particles (catalyst charging in the vertical reactor directly connected to the reaction tube on top of the preheating tube This makes it easy to have the effect of enabling stable operation.

1 is a schematic diagram illustrating a biooil supercritical water reforming reaction system having a vertical reactor according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the appended drawings illustrate only the contents and scope of technology of the present invention, and the technical scope of the present invention is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

1 is a schematic view showing a biooil supercritical water reforming reaction system having a vertical reactor according to an embodiment of the present invention.

As shown, the reaction system 10 according to the present invention includes a reactant input device 20, a vertical reaction device 30, and a post-treatment device 40.

The reactant input device 20 is a device for supplying the reactant mixed with the biooil and water received from the wood-based biomass to the vertical reactor 30. The reactant dosing device 20 is a cylindrical injector 21, the first water reservoir 22 and the reactant storage tank 23 for supplying water and the reactant to the cylindrical injector, and the cylindrical during initial operation It includes a preparatory water storage tank 24 for supplying water instead of the reactant to the injector.

The cylindrical injector 21 is provided with a cylinder 211 of a cylindrical body vertically entered, the inner space of the cylinder while moving up and down inside the cylinder of the upper reaction material chamber 214 and the lower The piston 212 partitioned by the water chamber 213 is provided.

At the upper end of the cylinder 211, the reactant supply pipe 215 is piped to supply the reactant filled in the reactant chamber to the vertical reactor 30, and the tubular body is located near the rear end of the cylindrical input device. An intermittent valve 216 for regulating the flow path is installed, and a pressure gauge is installed between the intermittent valve and the cylindrical injector to measure the pressure inside the pipe.

The first water storage tank 22 is to inject water into the water chamber 213 that is the front end of the cylinder through the water injection pipe 221 to the storage tank is installed on the balance (digital balance). The water injection pipe 221 is provided with a high-pressure pump 222 is installed on the line to supply the stored water at a high pressure, and to install an intermittent valve 223 on the line to intercept the internal flow path. In addition, the water injection pipe 221 is further installed between the flow control pipe 224 between the intermittent valve 223 and the front end of the cylinder installed on the line to the water discharged from the water chamber when the reactant filling the reactant chamber 214 When the water is supplied to the water chamber 213 through the water injection pipe 221 by installing an intermittent valve 225 on the line in the flow pipe 224 to the first water storage tank 22 to be re-stored. Try to prevent water leaking through the return pipe.

The reactant reservoir 23 stores the reactant and fills it with the reactant chamber 214 of the cylindrical injector 21. The reactant storage tank 23 is connected to the cylindrical injector 21 through the reactant injection pipe 231, and the reactant injection pipe 231 is connected between the intermittent valve 216 and the rear end of the cylindrical input pipe of the reactant supply pipe. In communication, the intermittent valve 216 of the reactant supply pipe is injected in a closed state to allow the reactant chamber 214 to be filled. In addition, a high pressure pump 232 is installed on the line of the reactant injection pipe 231 to supply a high pressure of the reactant in the reactant storage tank, and an intermittent valve 233 is further installed on the line to provide the reactant in the reactant chamber. When supplied to a vertical reactor, prevent backflow through the reactant inlet line.

In addition, the reactant storage tank 23 receives the bio-oil stock solution and water from the stock solution storage tank 234 and the second water storage tank 235 to make up for the shortage due to the supply, thereby enabling continuous supply. That is, the stock solution and water are transferred by a pump to be added or mixed, respectively, and then introduced. The reactant storage tank 23 may be provided with a conventional stirring device so that the injected stock solution and water are well stirred. In addition, the stock solution storage tank 234 and the second water storage tank 235 may be supplied with the required stock solution and water through a separate stock transfer pipe and a water replenishment pipe when the amount of storage decreases because the scale is installed at the bottom.

In addition, the preliminary water storage tank 24 temporarily supplies water instead of the reactants to create a temperature and pressure in the supercritical water environment during the initial operation before supplying the reactants to the vertical reactor 30. Is stored. The preparation water storage tank 24 is connected to communicate with the reactant material supply pipe 215 by the preparation water supply pipe 241. The preparation water supply pipe and the reactant supply pipe are combined using a tee as shown, and the preparation water supply pipe line includes a high pressure pump 242 for high pressure transfer of the preparation water and an intermittent valve for intermitting the preparation water supply pipe. ) If necessary, open the control valve and supply high pressure water from the preparation water storage tank.

Next, the vertical reactor 30 preheats the reactant to be introduced and reformates the preheated reactant under supercritical water to produce a product containing combustible syngas.

The vertical reactor 30 has a vertical reactor 31 which is a vertical cylinder. The vertical reactor is formed with a catalyst support 313 protruding along the inner circumferential surface of the middle portion, the metal mesh 314 is placed on the catalyst support. The inside of the vertical reactor is divided into an upper reaction chamber 312 and a lower preheating chamber 311 by the metal mesh, and a reactant supply pipe 215 communicates with a lower side of the preheating chamber, and an upper discharge tube at the top of the reaction chamber. (39) is in communication with the reactants introduced into the preheat chamber to catalytic reforming reaction in the reaction chamber to discharge the product through the discharge pipe.

The internal heater 32 is installed in the axial direction inside the preheating chamber 311 of the vertical reactor, and a coil-type external heater 33 is installed on the lower outer wall of the preheating chamber so that the reactant introduced therein is upward. The preheating is performed quickly while moving, and a thermocouple 34 is installed in the preheating chamber and the reaction chamber to measure the preheating temperature and the reaction temperature of the reactants.

In addition, the lower end of the vertical reactor 31 is in communication with the preheating chamber, the solid storage tank 35 is integrally formed. The solids storage tank 35 is a chamber for storing solids that are generated by side reaction (coking) while the reactant is heated and settled by its own weight. The solids storage tank may be equipped with a separate discharge pipe on one side to be discharged when a certain amount is stacked.

In addition, the reaction chamber 312 of the vertical reactor 31 forms a catalyst layer 36 by filling a catalyst on an upper portion of the metal network 314 so that the reactant reacts with the catalyst in a supercritical water condition. A disk-shaped filter 37 covering the vertical reactor is installed on the catalyst layer to prevent the catalyst from flowing out due to suspension. Various catalysts may be used as the catalyst to be charged, but preferably, Ni-Y / AC catalyst is used. It is used after charging.

In addition, a heating furnace 38 is installed on the outer surface of the vertical reactor. The heating furnace includes a vertical reactor 31 and heats both the preheating chamber and the reaction chamber inside the vertical reactor to increase the temperature.

The vertical reactor 31 may be provided in a form in which the preheating chamber and the reaction chamber are separated into each preheating tube and the reaction tube, and connected and integrated with each other by a union or a reducer. In this case, the connecting portion may use the inner protruding portion as the catalyst layer support in which the metal network is placed, so that the stacking of the catalyst may be performed.

On the other hand, the after-treatment device 40 is a device for producing a synthesis gas from which foreign substances are removed by cooling and phase-separating the product produced in the vertical reactor.

The post-treatment device 40 includes a heat exchanger 41 for cooling a product generated in the vertical reactor 30 to room temperature, a cylindrical filter 42 for filtering solids from the product cooled by the heat exchange, and the A post pressure controller 43 for reducing the reaction pressure of the product from which the solids are separated and an atmospheric pressure and a gas-liquid separator 44 for separating the reduced pressure product into a gas phase and a liquid phase are sequentially installed.

In addition, the gas-liquid separator 44 is provided with a circulating pipe 441 in communication with the lower portion, and the intermittent valve 442 is installed on the flow path of the circulation pipe to control the separated liquid outflow water level in the gas-liquid separator, and the excess effluent discharged is Transfer to the second water storage tank 235 may be reused in the production of reactants.

In addition, the gas flow meter 45 for measuring the gas flow rate may be installed in the pipe line for discharging the gas gas separated from the gas-liquid separator.

In addition, a pressure gauge may be installed in each line to check the reaction pressure. For example, by installing a pressure gauge at the rear end of the reactant supply pipe and the cylindrical filter, the reaction pressure difference before and after the vertical reactor in which the reforming reaction is performed can be confirmed.

Such a biooil supercritical water reforming reaction system having a vertical reactor according to the present invention and a method of operating the same,

First, all the detailed devices including the vertical reactor 30 filled with the catalyst are connected by a high pressure tube to form a flow path of the reaction system at a high pressure, and then the intermittent valve 243 of the preparation water supply pipe 241 is opened, and the cylinder type is The intermittent valve 216 installed in the reactant supply pipe 215 at the rear end of the injector 21 is closed so that the water of the preparation water storage tank 24 is supplied to the vertical reactor 31 by the high pressure pump 242.

The after pressure controller 43 of the aftertreatment device 40 maintains the normal pressure and completely opens the valve so that the water supplied to the lower portion of the vertical reactor 31 is introduced into the gas-liquid separator 44 through the upper portion of the vertical reactor. Close the solids storage tank 35 at the bottom of the vertical reactor 31 and the intermittent valve 442 installed at the gas-liquid separator 44 so that water does not flow out to the outside, thereby reducing the pressure and temperature of the vertical reactor reaction chamber 312. Increase to supercritical conditions.

In addition, the reactant storage tank 23, the pre-stored bio-oil stock solution is introduced into the reactant storage tank 23 using a pump from the stock solution storage tank 234, and the water is pumped from the second water storage tank 235 for dilution. Through the reactant reservoir at the same time. The amount of inflowing biooil and water is measured through a scale installed in each reservoir 234, 235 to control the inflow amount so that a reactant having a desired concentration of organic matter is prepared. For this purpose, it is necessary to analyze and know the concentration of organic material in bio oil in advance. There are hundreds of organic compounds in biooil, so it is very difficult to accurately measure their amount. Therefore, the chemical oxygen demand (COD), total organic carbon (TOC), and water content are measured to determine the concentration of total organic matter, and the effluent sample obtained after the experiment is subjected to the same analysis to calculate the degree of gasification of organic matter. do. A homogeneous single phase reactant is prepared by mixing the introduced biooil and water well using an agitator installed in the reactant storage tank 23.

The water chamber 213 of the cylindrical feeder 21 is filled by supplying water from the first water storage tank 22 to the high pressure pump 222, and the amount of water introduced is calculated by using a scale of the first water storage tank. Add a volume of (213).

The reactant chamber 214 of the cylindrical type feeder supplies the reactant of the reactant reservoir 23 to the high pressure pump 232, but the reactant supply pipe 215 is a tee part which is joined to the preparation water supply pipe 241. To isolate the opening of the intermittent valve 216 between the rear end of the cylindrical injector and the separated end so that the reactant material fills the reactant chamber 214 and flows to the separated end, the intermittent valve 216 is closed and the separated reaction. After the substance supply pipe 215 is connected, the reaction material is stopped.

While the intermittent valve 225 of the circulating pipe 224 is closed, the water in the first water reservoir 22 is continuously supplied to the water chamber 213 of the cylindrical input machine to raise the piston 212 to increase the pressure of the reactant chamber. The reaction pressure is increased, and when the pressure is completed, the intermittent valve 223 of the water injection pipe is closed and the water is stopped to allow the reactant to be introduced into the vertical reactor 31.

Meanwhile, the water of the preparation water storage tank 24 is supplied to the lower preheating chamber 311 of the vertical reactor and vertically rises to pass through the aftertreatment device 40 through the reaction chamber, and the gas-liquid separator 44 of the aftertreatment device. When water flows into the furnace, the pressure between the high pressure pump 242 and the after pressure controller 43 of the water supply line is increased by using the after pressure controller 43 to the reaction pressure.

In addition, the internal heater 32, the external heater 33, and the heating furnace 38 installed in the preheating chamber 311 are operated to maintain the preheating chamber temperature at 500 ° C or higher, and the reaction chamber temperature at 600 ° C or higher. To be maintained. In addition, the amount of stored water of the preparation water storage tank 24 is measured at regular intervals with a scale to measure the flow rate of the introduced water, and is set to be equal to the flow rate of the reactant to be supplied to the after pressure controller 43 and the preparation water supply pipe 241. ) And the water injection pipe 221 is maintained at the same reaction pressure to complete the preparation necessary for the reforming reaction.

When the preparation is complete, close the intermittent valves 243, 233 and 225 of the preparation water supply pipe 241, the reactant injection pipe 231 and the circulating pipe 224, and open only the intermittent valve 223 of the water injection pipe 221, and then the high pressure pump 222. Preheat chamber of the vertical reactor through the reactant supply pipe 215 through the reactant supply pipe 215 by supplying the water of the first water storage tank 22 to the water chamber by pushing the piston 212 By supplying to the (311) it is to perform the synthesis gas production operation by the reforming reaction of the bio-oil.

In the preferred method of the present invention, the organic material concentration of the reactant prepared by diluting the biooil and water is about 50,000-200,000 mgO ₂ / L based on COD, and the preheating chamber of the vertical reactor is 500-. The preheating temperature of 650 ℃, the reaction chamber is operated by supplying the reactants at the reaction temperature in the range of 650-710 ℃, reaction pressure in the range of 25-35 MPa, inflow rate of 25-50 h-1 LHSV.

Unlike the conventional supercritical water reforming or gasifier, the biooil supercritical water reforming reactor is characterized in that the reaction chamber and the preheating chamber are vertically connected, and the flow of the reactants flows from the bottom to the top in the opposite direction to the gravity direction. . Therefore, the solids generated by coking during the preheating of the reactants may be separated from the reactants by gravity settling in a solids storage tank installed at the bottom of the preheating chamber.

In addition, since it is possible to prevent the catalyst layer closing phenomenon and the catalyst surface activity decrease which are a problem in a general fixed bed reactor, it is possible to prepare and use a reactant having a higher concentration of organic matter.

According to the embodiment, a reactant having a chemical oxygen demand (COD) of about 200,000 mgO ₂ / L may also be treated using the vertical reactor of the present invention. In order to perform the reforming reaction more effectively, it is preferable to prepare a catalyst which is active in the relevant reaction and use it in a reactor, but the catalyst used in the present invention is not limited. Therefore, it is possible for the operator to adjust the reforming reactor by selecting the reactor catalyst layer as needed.

Hereinafter, an embodiment of producing a combustible synthesis gas by reforming a supercritical water of a biooil diluted in water by a reaction system having a vertical reactor according to the present invention and an operation method thereof.

Example 1 Catalyst Influence

The catalyst effect on the production of flammable syngas by supercritical water reforming of the biooil using the reaction system having the vertical reactor of FIG. 1 is shown in [Table 1].

In the embodiment of the present invention, LHSV was defined as a value obtained by dividing the reactant inflow rate by the reactor volume at room temperature, and the higher this value, the shorter the reaction time. Therefore, in LHSV, the residence time of the reactants in the preheat chamber was not taken into account.

The main operating conditions of this embodiment are described in Table 1 below, and as shown in Table 1, the total gas generation rate was high in the nickel-itrium / active charcoal (Ni-Y / AC) catalyst reaction, and the generated gas composition was analyzed. As a result, the contents of hydrogen and carbon dioxide are high and the contents of carbon monoxide and low hydrocarbon are low.

These results show that the Ni-Y / AC catalyst has activity in the hydrogen production reaction. Activated charcoal (AC) was also somewhat active in the hydrogen production reaction, but did not significantly affect the total gas production rate.

As a result of measuring the calorific value of the generated gas, high values were obtained in the order of no catalyst>AC> Ni-Y / AC catalyst. This is because carbon monoxide, methane, and lower hydrocarbons, which have high calorific value, were produced more in the absence of catalyst or AC catalyst. As a result of measuring the chemical oxygen demand (COD) of the liquid product, the COD removal rate was much higher in the Ni-Y / AC case, and the AC was similar to the case without the catalyst.

 * Other operating conditions;

-Initial concentration of reactant: 145,840 mgO ₂ / L based on chemical oxygen demand (COD),

PH of reactant: about 2.5,

Preheat chamber temperature: 590-650 ℃

-Reaction chamber temperature: 670 ℃,

-Reaction pressure: 28 MPa,

-Rate of reactant in the vertical reactor: 25 h ^-1 LHSV

Example 2 Initial Concentration Effect of Reactants

The results of the supercritical water reformation according to the organic concentration of the reactants prepared by diluting the biooil stock solution are shown in [Table 2].

As the initial concentration of the reactants increased, the total gas generation rate and the generated gas calorific value increased. The hydrogen content of the product gas decreased with increasing initial concentration of the reactants, while the content of other gases tended to increase. This is because the higher the reactant concentration, the lower the hydrogen production reaction rate. In particular, comparing the content of hydrogen and methane, it can be seen that the decrease in hydrogen content is due to the reduction rate of methane reforming reaction.

However, as can be seen from the result of removing the high chemical oxygen demand (COD) of the liquid phase, using the present invention gasification of high concentration biooil of about 200,000 mgO ₂ / L of 96% or more gas to generate a high calorific value of about 3,800 kcal / Nm ³ Can produce a clean flammable gas.

This calorific value corresponds to at least twice the calorific value of the gas produced from the conventional partial oxidation gasification reactor. The pH of the reactants was considerably acidic (2.5), but the pH of the liquid product was neutral (6-8), because most of the acidic substances in the reactants such as organic acids were gasified during the supercritical water reforming process. .

* Other operating conditions;

PH of reactant: about 2.5,

Catalyst: nickel-itrium / active char (Ni-Y / AC),

Preheat chamber temperature: 590-650 ℃

-Reaction chamber temperature: 670 ℃,

-Reaction pressure: 28 MPa,

-Reactor reactant inflow rate: 25 h ^-1 LHSV

Example 3: Effect of Reactant Dosing Rate

The results of supercritical water reforming of biooil according to the reactor feed rate of the reactants are shown in [Table 3].

Although described in Example 1, LHSV is defined as a value obtained by dividing the reactant inflow rate at the reactor temperature by the reactor volume. The higher this value, the shorter the reaction time.

In Table 3, LHSV 25 h ^{−1 corresponds} to 180 g / h and 50 h ⁻¹ corresponds to 360 g / h.

The total gas generation rate and the generated gas calorific value tended to increase with increasing reactant input flow rate, but the product gas composition did not change significantly.

Therefore, it is determined that the reactant input flow rate does not significantly affect the supercritical water reforming results under the experimental conditions. This is an encouraging result, meaning that more biooil can be treated with the device of the present invention.

* Other operating conditions;

Initial concentration of reactant (COD): 74,000 mgO ₂ / L,

pH: about 2.5,

Catalyst: nickel-itrium / active char (Ni-Y / AC),

Preheat chamber temperature: 590-650 ℃

-Reaction chamber temperature: 675 ℃,

-Reaction pressure: 28 MPa

Example 4: Reaction Temperature Influence

The effect of reaction temperature on the supercritical water reforming of biooil is shown in [Table 4].

As the reaction temperature of the catalyst bed increased, the total gas generation rate increased, but the increase rate tended to decrease as the temperature increased. This is because, as the COD removal rate shows, most of the organic material was gasified when the reaction temperature reached about 650 ℃.

However, as shown in [Table 4], the dependence of the reaction temperature on the gasification rate tended to be different depending on the initial concentration of the reactants. In other words, the higher the initial concentration of the reactants, the stronger the temperature dependence of the total gas production rate at high temperatures, and the weaker the initial concentration.

The calorific value of the product gas increased with increasing reaction temperature and then decreased significantly above 680 ℃. This is because, as shown in the product gas composition, the hydrogen production reaction is activated at high temperature, and the hydrogen production amount is increased and the content of high calorific gases such as methane, ethane, and propane is decreased.

The optimum reaction temperature can be determined according to the purpose of use of the produced gas. For example, if you want to use the generated gas as the fuel for power generation, the temperature near 650 ℃ where the calorific value shows the maximum is the optimal temperature, and if you want to use the generated gas as the raw material for hydrogen production, the reactor is operated It is preferable.

* Other operating conditions:

PH of reactant: 2.5,

Catalyst: nickel-itrium / active char (Ni-Y / AC),

Preheat chamber temperature: 509-665 ℃,

-Reaction pressure: 28 MPa,

-Rate of reactant in the vertical reactor: 25 h ^-1 LHSV

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It can be understood that

10: reaction system
20: Reactant input device
21: cylinder type feeder 22: the first water storage tank
23: reactant storage tank 24: preparation water storage tank
211 cylinder 212 piston
213: water chamber 214: reactant chamber
215: reactant supply pipe
216,223,225,233,243,442: intermittent valve
221: water injection pipe 222,232,242: high pressure pump
224: flow pipe
231: reaction material injection pipe 234: stock solution tank
235: second water storage tank
241: preparation water supply pipe
30: vertical reactor
31: vertical reactor 32: internal heater
33: external heater 34: thermocouple
35: solids storage tank 36: catalyst bed
37 disc shaped filter 38 heating furnace
39: discharge pipe
311: preheat chamber 312: reaction chamber
313 catalyst support 314 metal mesh
40: post-processing device
41: heat exchanger 42: cylindrical filter
43: after pressure controller 44: gas-liquid separator
45: flow meter
441: circulation pipe

Claims (10)

A reactant input device 20 for inputting a reactant mixed with biooil and water received from woody biomass; A vertical reactor 30 for preheating the injected reactant and reforming the preheated reactant under supercritical water to produce a product containing combustible syngas; And a post-treatment device 40 for producing a synthesis gas from which foreign matters are removed by cooling and phase-separating the product produced in the vertical reactor.
The reactant injection device 20,
A cylindrical injector 21 whose interior is partitioned into a reactant chamber 214 and a water chamber 213 by a piston 212;
A first water storage tank 22 having a scale installed at a lower portion of the water stored by the high pressure pump 222 to transfer the high pressure water to the water chamber through the front end of the cylindrical feeder;
The reactants are prepared by agitating and receiving bio-oil stock solution and water from the stock solution storage tank 234 and the second water storage tank 235 in which the scale is installed, and the prepared reactant is connected to the rear end of the cylindrical type feeder by a high pressure pump 232. Reactant storage tank 23 to be filled into the reactant chamber 214 through;
Characterized in that consisting of; a pre-water storage tank 24 is stored to supply the water instead of the reactant to form the inside of the vertical reactor in the supercritical water environment during the initial operation before supplying the reactant to the vertical reactor Biooil supercritical water reforming reaction system. delete According to claim 1, wherein the cylindrical input machine 21,
A cylinder 211 of a vertical cylinder;
A piston 212 dividing the cylinder internal space into a reactant chamber 214 and a water chamber 213;
A reactant supply pipe 215 piped to the rear end of the cylinder and supplying the reactant filled in the reactant chamber 214 to the vertical reactor 30;
A reactant injection pipe 231 installed in communication with the reactant supply pipe at the rear end of the cylinder to inject the reactant into the reactant chamber 214 of the cylinder;
A water injection pipe 221 for injecting water from the first water storage tank 22 into the water chamber 213 at the front end of the cylinder;
A circulating pipe 224 communicating with the water injection pipe 221 at the front end of the cylinder and re-transmitting the water discharged by the filling of the reactant to the first water storage tank 22;
Bioreactor supercritical water, characterized in that consisting of the reaction material supply pipe 215, the reaction material injection pipe 231, the water injection pipe 221, the control valve 216, 233, 223, 225, respectively installed in the return pipe 224 Reforming reaction system. The method of claim 1, wherein the vertical reactor 30,
In the middle of the vertical cylinder, a catalyst support 313, which is a step protruding from the central axis along the inner circumferential surface, is formed, and the catalyst support is placed in the upper reaction chamber 312 and the lower preheating chamber 311 by placing a metal mesh 314 therein. And a vertical reactor (31) communicating with the reactant supply pipe (215) at the lower side of the preheating chamber and communicating with a discharge pipe (39) at the top of the reaction chamber;
An internal heater (32) disposed in the preheating chamber to heat the reactants;
An external heater 33 installed in a coil form on an outer wall of the preheating chamber to heat the reactant introduced;
A thermocouple 34 disposed in the preheating chamber and the reaction chamber to measure a preheating temperature and a reaction temperature of a reactant;
A solids storage tank 35 communicating with the bottom of the vertical reactor and storing solids which are generated as a side reaction (coking) and settle as the reactants are heated;
A catalyst layer 36 filling the upper portion of the metal mesh of the reaction chamber;
A disk-shaped filter 37 installed on the catalyst layer to prevent the outflow of the catalyst by floating;
And a heating furnace (38) installed to enclose the vertical reactor to heat the vertical reactor. The method of claim 4, wherein the vertical reactor 31,
The preheating chamber and the reaction chamber are separated into each preheating tube and the reaction tube, and are integrated by connecting with a union or reducer.
A biooil supercritical water reforming reaction system, characterized in that the inner protruding portion of the connection portion is used as a catalyst layer support on which a metal network is placed. According to claim 1, The post-processing device 40,
A heat exchanger (41) for cooling the product discharged from the vertical reactor to room temperature;
A cylindrical filter 42 for filtering solids from the product cooled by heat exchange;
A post pressure controller (43) for reducing the reaction pressure of the product from which the solids are separated to atmospheric pressure;
A gas-liquid separator 44 for separating the reduced pressure product into a gas phase and a liquid phase;
A circulation pipe 441 which is connected to the gas-liquid separator and regulates the liquid effluent water level, and controls the excess effluent to the second water storage tank 235, and an intermittent valve 442 is installed;
Biogas supercritical water reforming reaction system, characterized in that it comprises a ;; syngas flow rate measuring device for measuring the synthesis gas production flow rate of the gaseous product (45). Cylindrical injector to store reactant in one space divided by piston and to inject water into the other space by injecting water into the other space, and to prepare water for supplying water instead of reactant at initial operation A reactant input device having a reservoir; A vertical reactor for raising the reactant introduced from the lower part while preheating the upper part to produce a syngas product by a catalytic reforming reaction under supercritical water conditions; In the operation method of the supercritical water reforming reaction system comprising a post-treatment device for generating a synthesis gas by removing the foreign matter of the product produced in the vertical reactor,
Initial operation method of the reaction system,
After forming the flow path of the reaction system at high pressure, the intermittent valve of the preparation water supply pipe is opened, and the intermittent valve installed at the reaction material supply pipe at the rear end of the cylinder type feeder is closed and the water of the preparation water storage tank is supplied to the vertical reactor by the high pressure pump. Make sure,
The after pressure controller of the aftertreatment device maintains the atmospheric pressure and opens the valve completely so that the water supplied to the lower part of the vertical reactor is introduced into the gas-liquid separator through the upper part of the vertical reactor, but the injected water is prevented from flowing out to the outside. Close all intermittent valves installed in the solid storage tank and the gas-liquid separator to raise the reaction chamber pressure and temperature in the upper part of the vertical reactor to supercritical water conditions.
Operation method of the reactant injection device,
Fill the water chamber of the cylindrical feeder by supplying the water of the first water storage tank with a high pressure pump,
The reactant chamber of the cylinder type feeder supplies the reactant material of the reactant reservoir with a high-pressure pump, but the reactant supply pipe separates the tee connected to the preparation water supply pipe to control the intermittent valve between the rear end of the cylindrical feeder and the separated end. When the reactant is filled with the reactant chamber and flows to the separated end, close the control valve, connect the separated reactant supply pipe, and stop the input of the reactant.
With the intermittent valve closed, the water in the first water reservoir is continuously supplied to the water chamber of the cylinder type feeder and the piston is raised to raise the pressure of the reactant chamber to the reaction pressure. A method of operating a supercritical water reaction system, characterized in that the closing of the valve and stopping the introduction of water to introduce the reactants into the vertical reactor. delete The method of claim 7, wherein the operation of the vertical reactor,
The water from the preparatory water storage tank is supplied to the preheating chamber under the vertical reactor and rises vertically to pass through the aftertreatment device through the reaction chamber.When water flows into the gas-liquid separator of the aftertreatment device, Increase the pressure between the high pressure pump and the after pressure controller to the reaction pressure,
The internal heater, the external heater and the heating furnace installed in the preheating chamber are operated to maintain the preheating chamber temperature above 500 ° C.,
The amount of water stored in the preparatory water storage tank is measured at regular intervals to measure the flow rate of the input water, and set to be equal to the flow rate of the reactant to be supplied so that the pressure between the after pressure controller, the preparative water supply pipe, and the water supply pipe is the same. To maintain pressure,
Close the intermittent valves of the preparation water supply pipe, the reactant injection pipe, and the circulating pipe, open only the intermittent valve of the water injection pipe, supply the water of the first water storage tank to the water chamber using a high pressure pump, and push the piston to push the reaction into the reaction chamber. A method of operating a supercritical water reaction system, characterized in that material is supplied to a preheating chamber of a vertical reactor through a reactant supply pipe. The method of claim 7, wherein the operating method of the supercritical water reforming reaction system,
The organic matter concentration of the reactants prepared by diluting the biooil and water is about 50,000-200,000 mgO ₂ / L based on COD,
The preheating chamber of the vertical reactor supplies the reactants at a preheating temperature of 500-650 ℃, the reaction chamber of 650-710 ℃, the reaction pressure in the range of 25-35 MPa and the inflow rate of 25-50 h-1 LHSV. Method for operating a supercritical water reforming reaction system, characterized in that the operation.

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