KR101769710B1 - bio heavy fuel oil production system with temperature controller using dry air - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a technology for refining and reusing a fuel flow channel satisfying the quality standards of biofuel feedstock and maintaining the animal and breakfast properties. More particularly, To provide a process for producing biofuel for power generation with low unit cost. In order to construct a low-cost production and operation facility for production of bio-fuel oil for power generation from palm oil by-products, an enzyme reactor is applied to a process for removing free fatty acid, and water content in the raw material and bio- An efficient air circulation type water removal process is provided at a low cost without using a vacuum dehydration and a vacuum distillation system as an apparatus for removing the gas phase and the liquid phase, Thereby providing a double circulating bio fuel oil production system.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a bio-fuel oil production system equipped with a dry air heat exchanger,

TECHNICAL FIELD The present invention relates to a technique for refining and reusing a fuel flow channel satisfying the quality standards of biofuel feedstock for maintaining the animal and breakfast properties, and more particularly, to a process for efficiently refining and purifying feedstocks from crude palm oil, Liquid double-loop type bio-fuel oil production system for producing high-quality fuel oil.

1. Bio-oil production technology

Recently, in order to fulfill the obligatory supply of energy through the implementation of the RPS (Mandatory Renewable Energy System), various generations of bio-energy are being promoted. The pilot project for bio-fuel oil for power generation is being carried out by four domestic power generation companies and the Korea District Heating Corporation, and is being manufactured and delivered under the management of the Korea Petroleum Management Authority at the factory of bio-diesel supplier and maintenance company . Bio-fuel oil for domestic power generation is mainly produced by refining and mixing low-cost raw materials such as palm oil, high-value-added palm by-product, biodiesel process by-product and animal oil to meet quality standards.

Currently, domestic and overseas industrial fuel oil production technologies are mostly producing industrial fuel oil using ion purification, reduced pressure distillation or pyrolysis process.

Ion refining method is a method to produce products by removing moisture and sediments from animal and vegetable oil and removing heavy metals etc. through chemical treatment. The produced product can be used only bunker C oil alternative fuel oil. Ion refining method is difficult to effectively remove ash, etc., often causing nozzle clogging, and the amount of residual carbon is also high. The process is complicated and the technology is rarely used in advanced countries due to its classical technology. The yield is about 70%.

The vacuum distillation process is a simple physical purification process. The yield of the vacuum distillation is about 70%, and a high temperature operation temperature is required to increase the yield. In addition, there is a drawback that the plant design cost is very high.

The high-temperature pyrolysis method is a method of producing bio-heavy oil by decomposing and condensing at a low molecular weight by applying heat at a temperature of 400 ° C or more and high pressure by blocking contact with air. The high-temperature pyrolysis process has a disadvantage in that odor is generated during operation, and the process is complicated and requires a long cleaning operation time, a continuous process is difficult, and a yield is relatively low. In addition, a device using a membrane separation system is being developed.

A raw material for producing power biofuel heavy oil is proposed by extracting oil from coconut husk and using remaining scrap, a pitch produced after biodiesel and biodiesel production, or a method using the vegetable oil.

Among these raw materials, palm oil by-products are considered to be the most competitive in terms of unit price and raw material supply and demand.

Bio-fuel oil for power generation shall meet the following quality standards as fuel for power generation boilers.

Item

Quality standards

Flash point (℃)
70 or more
Kinematic viscosity (40 캜, mm 2 / s)
20 ~ 100
Residual carbon content (% by weight)
below 10
Sulfur (weight%)
0.1 or less
Ash (weight%)
0.10 or less
Copper corrosion (50 ℃, 3h)
1b or less
Pour Point (℃)
27.5 or less
Density (15 캜, kg / m 3)
991 or less
Moisture (% by weight)
0.20 or less
Calculated value (mg KOH / g)
25 or less


Alkali metal (mg / kg)
Na
70 or less
Ca
30 or less
K
70 or less
Iodine (g / 100 g)
120 or less
Nitrogen (% by weight)
0.3 or less
Vanadium (mg / kg)
Less than 50
Calorific value (kcal / kg)
More than 9,000
Water and sediment (vol%)
0.5 or less
Silicon + aluminum + iron (mg / kg)
200 or less
Phosphorus (mg / kg)
Below 100

One of the most important processes in the production of biofuel is the process of removing moisture.

 Among the about 22 quality standards of biofuel for power generation, moisture should be kept at 0.2 wt% or less in the whole biofuel.

Moisture is present in various amounts depending on the kind of raw material to be fed. In addition, as the amount of total moisture including water generated as a by-product increases during the esterification reaction, the reaction yield is lowered. In addition, Water is one of the impurities that must be removed. However, as mentioned above, the process for removing moisture at present requires vacuum dewatering and vacuum distillation at a high temperature, which requires expensive equipment for a lot of energy and decompression.

In order to separate and treat the leachate in the waste oil through the independent evaporator, ESTIX Shipbuilding & Marine Engineering Co., Ltd. uses the specific gravity difference between water and oil to determine leachate in the waste oil tank (KR 10-2013-0099615 A). In addition, it is possible to remove the leachate by heating. Bugang Tech Co., Ltd. has developed a waste oil refining system using a separation membrane process to remove moisture and volatile impurities in waste oil by preheating and heating the waste oil (KR 10-2011-0088058). Sewa ENSTECH Co., Ltd. applied Vacuum Evaporation technology (KR 10-1023958 B1) to separate oil and water in the process of treating oil-containing wastewater from the waste oil recycling process. Samyoung Piltech Co., Ltd. has proposed a technology using evaporation chamber provided with a perforated plate having a number of holes at the lower part of the injection nozzle to improve the efficiency of water removal in a mobile waste oil purifier (KR 10-0863154 B1).

2. Adsorption of water

Adsorption is a phenomenon in which molecules of the gas stagnate at the interface between the adsorbent and the adsorbent, and the adsorption is usually attributed to the surface adsorption on the inner wall of the adsorbent and the condensation on the inner wall of the adsorbent. The surface adsorption is also called chemical adsorption.

Commercially available adsorbents that are inexpensive in solid-type moisture adsorbents include silica gel and zeolite.

Silicagel is a jelly form obtained by adding an inorganic acid to an aqueous solution of sodium silicate, which is washed and dried. It is mainly composed of silicic acid (SiO ₂ ). It is chemically stable and colorless and harmless. The silica gel is porous and has a uniform pore distribution. Inside there are innumerable capillaries of ²⁰ ~ 80X10 ^-8 cm. The capillary surface area is 200 to 800 m 3 / g and the capillary volume is 0.4 to 0.6 cc / g.

The adsorption power against moisture is so great that it can adsorb moisture up to 40% of its own weight. Theoretically, the lowest equilibrium dew point can be obtained up to -70 ° C. For regeneration, it takes two hours at 150 to 180 캜. Even after regeneration, about 5% of the moisture is chemically bonded, and the dry weight of the silica gel, which usually contains 5% water, is used.

1,100 to 1,400 kPa / h is required for 1 kg of water desorption, and the adsorption capacity is lost if heated to 260 ° C or more.

Activated alumina is a porous alumina trihydrate prepared by heat treatment of alumina hydrate, and it mainly consists of alumina (AI ₂ O ₃ ). The residual moisture content is 7% and has high mechanical strength against impact and friction. The moisture adsorption capacity is about 13 ~ 15%, and the lowest equilibrium dew point can reach -76 ℃. At the time of regeneration, it is heated to 175 to 250 캜.

Since the specific surface area of the alumina body obtained by heat-treating the alumina hydrate is limited, silica gel may be added in order to improve the performance as an adsorbent. Addition of silica gel is very excellent as an adsorbent for dehumidification because it prevents crystallization of alumina, increases specific surface area, increases activity and heat resistance, and lowers regeneration temperature.

Synthetic zeolites (Molecular Sieves) have been known for a long time as natural minerals. They have been developed by Union Carbide of the USA and have a wide range of uses as molecular sieves. Molecular Sieves is a surface adsorption type adsorption isotherm due to a sieve. It has a large adsorption capacity close to the saturation adsorption amount even under an extremely low water vapor partial pressure, and its drying property is extremely strong, which is why it is popular as a super-desiccant. The use of synthetic zeolite is used in highly drying processes using strong hygroscopicity due to its nature and molecular capture effect due to the pore structure of the three-dimensional network structure. For example, there are many applications such as water removal in the separation gas in the petrochemical field, production of LNG, production of liquefied carbon dioxide gas, and production of freon refrigerant. It is also widely used for adsorption and separation of chemical substances.

The above-mentioned solid adsorbents are mainly used in air dehumidifiers, and are selected according to the required outlet stalls or economics. In addition, the adsorption and desorption characteristics of each adsorbent should be carefully examined. For example, silica gel is superior to other adsorbents in terms of effective adsorption amount, but has a property of being broken when brought into direct contact with water. However, since the regenerated heat capacity can be regenerated with a low energy, it is suitable for a heating and dehumidifying device.

3. Non-aqueous reaction for esterification

Triacylglycerol acylhydrolase (EC 3.1.1.3) is an enzyme that hydrolyzes glycerides to fatty acids and glycerol. Lipase is characterized not only in vivo but also ex vivo in other ester compounds, and is useful in the field of organic synthesis. In particular, lipase can serve as a catalyst for the esterification reaction, which is a reverse reaction of hydrolysis, and has been used as a catalyst useful in the esterification reaction under non-aqueous reaction conditions.

Reactions using lipase are shown in the figure below.

R ₁ COOR ₂ + R ₃ OH ----- (lipase) -> R ₁ COOR ₃ + R ₂ OH

1. Hydrolysis reaction: R ₂ = R, R ₃ = H

2. Esterification: R ₂ = H, R ₃ = R

3. Transesterification: R ₂ = R, R ₃ = R '

In the chemical reaction formula, the hydrolysis reaction and the esterification reaction are reversible reactions. In the hydrolysis reaction, water is used as a substrate and in the esterification reaction, water is produced as a product or a by-product. Therefore, chemical equilibrium is also shifted depending on the amount of water, so in order to maximize the conversion rate of the esterification reaction, it is necessary to remove generated water. It is evident that enzymes for the esterification reaction can utilize various kinds of enzymes other than lipase, including esterases.

An object of the present invention is to provide a process capable of producing bio-fuel oil for power generation with low cost by providing the most economical raw materials at the time of manufacturing bio-fuel oil for power generation.

Another object of the present invention is to provide a technique for applying an enzyme reactor to a process for removing free fatty acids to construct low-cost production and operation facilities for producing biofuel heavy oil for power generation from coconut oil byproducts.

The present invention relates to an apparatus for removing water generated in a biofuel manufacturing process or a raw material for a biofuel such as crude animal care or maintenance of physical properties of a bird as described above, And an object of the present invention is to provide an efficient air circulation type moisture removal process.

It is another object of the present invention to minimize the emission of odors generated in raw materials of biofuels into the atmosphere by disposing an air scent remover in the circulation process for removing moisture.

It is another object of the present invention to provide a system for controlling each of the above objects so as to optimize the respective objectives by simultaneously performing the water removal and the acid elimination reaction, thereby remarkably increasing the yield of the esterification reaction.

The present invention relates to a bioreactor comprising raw material tanks (1,2,3), a mixer (7), a main reactor (4), an enzyme reaction reactor (12) for deoxidation, a moisture removing device (13,14) In the heavy oil production system, the raw material tank includes a first raw material tank 1 storing PAO (Palm Acid Oil), a second raw material tank 2 storing a CNSL (Cashew nut Shell Liquid), and a BP (Bio-Pitch) And a third raw material tank (3) stored therein; A mixer (7) in which a raw material supplied from the first, second and third raw material tanks and a catalyst for degumming are added and mixed; A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature; A reactor for esterifying free fatty acids with a portion of the liquid phase of the main reactor being circulated is characterized in that the esterification enzyme immobilized on the carrier is composed of a packed-bed type, and the inlet is provided with a lower alcohol for the esterification reaction An enzyme reaction reactor 12 for deoxidation, which comprises a component as a constituent; A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated; A malodor removing unit (17) for removing volatile odor components in the dry air from which moisture has been removed through the water removal unit; And a base heat exchanger (20) for controlling the temperature of the dry air through the malodor remover (17) to assist in controlling the temperature of the main reactor, wherein the atmospheric heat exchanger (20) is disposed below the main reactor And a dry air supply device in which dry air from which malodorous components have been removed is supplied for moisture stripping is disposed, wherein a moisture content is 0.02 to 0.2% by weight, an acid value is 2 to 25, and And a method for producing biofuel feedstock having a calorific value of 9,500 kcal / kg or more.

The present invention provides a process for producing biofuel heavy oil for power generation with low cost by providing the most economical raw materials at the time of manufacturing biofuel heavy oil for power generation.

Another effect of the present invention is to provide a technique for applying an enzyme reactor to a free fatty acid removal process for establishing a low-cost production and operation facility for producing biofuel feed oil from coconut oil byproducts.

The present invention relates to an apparatus for removing water generated in a biofuel manufacturing process or a raw material for a biofuel such as crude animal care or maintenance of physical properties of a bird as described above, It is possible to provide an efficient air circulation type moisture removal process.

Another effect of the present invention is to minimize the emission of odor generated in the raw material of the biofuel into the atmosphere by installing an air smell eliminator in the circulation process for removing water.

Fig. 1 Flow chart of biofuel oil production process
Fig. 2 Bio-heavy oil production system
3 is a schematic view showing a system for producing a liquid and a gas phase double-looped bio-oil according to the present invention
4 is a flowchart of the manufacturing process in the present invention
Fig. 5 Structure of a biofuel feedstock reactor

The present invention relates to a bioreactor comprising raw material tanks (1,2,3), a mixer (7), a main reactor (4), an enzyme reaction reactor (12) for deoxidation, a moisture removing device (13,14) In the heavy oil production system, the raw material tank includes a first raw material tank 1 storing PAO (Palm Acid Oil), a second raw material tank 2 storing a CNSL (Cashew nut Shell Liquid), and a BP (Bio-Pitch) And a third raw material tank (3) stored therein; A mixer (7) in which a raw material supplied from the first, second and third raw material tanks and a catalyst for degumming are added and mixed; A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature; A reactor for esterifying free fatty acids with a portion of the liquid phase of the main reactor being circulated is characterized in that the esterification enzyme immobilized on the carrier is composed of a packed-bed type, and the inlet is provided with a lower alcohol for the esterification reaction An enzyme reaction reactor 12 for deoxidation, which comprises a component as a constituent; A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated; A malodor removing unit (17) for removing volatile odor components in the dry air from which moisture has been removed through the water removal unit; And a base heat exchanger (20) for controlling the temperature of the dry air passing through the malodor remover (17) to assist in controlling the temperature of the main reactor, wherein the base heat exchanger (20) is disposed below the main reactor And a dry air supply device in which dry air from which malodorous components have been removed is supplied for moisture stripping is disposed, wherein the moisture content is 0.02 to 0.2% by weight, the amount of water is 2 to 25, and And a method for producing biofuel having a calorific value of 9,500 kcal / kg or more.

The present invention relates to a bioreactor comprising raw material tanks (1,2,3), a mixer (7), a main reactor (4), an enzyme reaction reactor (12) for deoxidation, a moisture removing device (13,14) In the heavy oil production system, the raw material tank includes a first raw material tank 1 storing PAO (Palm Acid Oil), a second raw material tank 2 storing a CNSL (Cashew nut Shell Liquid), and a BP (Bio-Pitch) And a third raw material tank (3) stored therein; A mixer (7) in which a raw material supplied from the first, second and third raw material tanks and a catalyst for degumming are added and mixed; A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature; And a deoxidation reactant supply unit for supplying a lower alcohol and an acid catalyst for the esterification reaction to the inlet for the esterification reaction of the free fatty acid as a part of the liquid phase of the main reactor is circulated; A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated; A malodor removing unit 17 for removing volatile odor components in the dry air from which moisture has been removed through the water removing unit, a temperature control unit for controlling temperature of the dry air passing through the malodor removing unit 17, Wherein a dry air supply unit is disposed in the lower part of the main reactor and in which dry air removed from the malodor component supplied from the malodor removing unit is supplied for moisture stripping. The present invention relates to a method for producing biofuel heavy oil having a moisture content of 0.02 to 0.2 wt%, a computer value of 2 to 25, and a heating value of 9,500 kcal / kg or more using a biofuel feed oil production system equipped with a heat exchanger.

The present invention relates to a process for producing a deodorant comprising a raw material tank (1,2,3), a mixer (7), a main reactor (4), an enzyme reaction reactor (12) for deoxidation, a moisture removing device (13,14) In a biofuel feed oil production system,

The raw material tank includes a first raw material tank 1 storing PAO (Palm Acid Oil), a second raw material tank 2 storing a CNSL (Cashew nut Shell Liquid), and a third raw material tank 2 storing BP (Bio-Pitch) 3); A mixer (7) in which a raw material supplied from the first, second and third raw material tanks and a catalyst for degumming are added and mixed; A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature; A reactor for esterifying free fatty acids with a portion of the liquid phase of the main reactor being circulated is characterized in that the esterification enzyme immobilized on the carrier is composed of a packed-bed type, and the inlet is provided with a lower alcohol for the esterification reaction An enzyme reaction reactor 12 for deoxidation, which comprises a component as a constituent; A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated; A malodor removing unit 17 for removing volatile odor components in the dry air from which moisture has been removed through the water removing unit, a temperature control unit for controlling temperature of the dry air passing through the malodor removing unit 17, And a dry air supply (19) which is arranged below the main reactor and in which dry air removed from the malodor component supplied from the malodor removing device is supplied for moisture stripping is disposed A moisture sensor or a main reactor in contact with the gaseous phase of the main reactor and the raw material tanks, and a moisture activity measuring sensor in contact with the liquid phase of each raw material tank, and the supply of air supplied to the water removal device And the rate of feed of the substrate supplied to the enzyme reaction reactor for deoxidation is controlled. The present invention relates to a method for producing biofuel having a moisture content of 0.02 to 0.2% by weight, an acid value of 2 to 25, and a calorific value of 9,500 kcal / kg or more.

The present invention relates to a process for producing a deodorant comprising a raw material tank (1,2,3), a mixer (7), a main reactor (4), an enzyme reaction reactor (12) for deoxidation, a moisture removing device (13,14) In a biofuel feed oil production system,

Wherein the raw material tanks each include two or more raw material tanks in which different raw materials are stored;

A mixer (7) in which two or more raw materials supplied from the two or more raw material tanks and a catalyst for degumming are added and mixed; A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature; A reactor for esterifying free fatty acids with a portion of the liquid phase of the main reactor being circulated is characterized in that the esterification enzyme immobilized on the carrier is composed of a packed-bed type, and the inlet is provided with a lower alcohol for the esterification reaction An enzyme reaction reactor 12 for deoxidation, which comprises a component as a constituent; A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated; A malodor removing unit 17 for removing volatile odor components in the dry air from which moisture has been removed through the water removing unit, a temperature control unit for controlling temperature of the dry air passing through the malodor removing unit 17, And a dry air supply (19) which is arranged below the main reactor and in which dry air removed from the malodor component supplied from the malodor removing device is supplied for moisture stripping is disposed A moisture sensor or a main reactor in contact with the gaseous phase of the main reactor and the raw material tanks, and a moisture activity measuring sensor in contact with the liquid phase of each raw material tank, and the supply of air supplied to the water removal device Characterized in that the rate of feed of the substrate supplied to the enzyme or the deoxygenation reactor is controlled EO heavy oil by using a manufacturing system, to a method for producing a 0.02 to 0.2% by weight water content, jeonsanga 2 to 25, and the heating value than 9,500 kcal / kg bio-oil-in-water.

According to the present invention, in the above liquid and vapor phase double-loop circulating biofuel feed oil producing system, an acidity sensor is provided on the liquid phase of the main reactor and each raw material tank, and the circulation rate of the deoxidation reactant / And the supply rate of the liquid phase bioreactor is controlled.

The present invention relates to the above-described gas-liquid and liquid-phase double circulation type heavy oil producing system, wherein the solid type moisture removing agent includes silica blue, and the water removing trap has a window And a moisture removal trap made of a transparent or translucent material, which is formed of a liquid or a liquid.

According to the present invention, in the vapor-phase and liquid-phase double circulating biofuel feed oil producing system, the dry air disperser (9) is disposed at one side of the lower portion of the tank or at the center or outside thereof, Liquid fractional biomass fuel oil production system capable of inducing circulation within the reactor by inducing the specific gravity of the portion to be lowered.

In the gas-liquid and liquid-phase double loop circulating biofuel feed oil producing system of the present invention, the main reactor may be any one of an air-lift reactor, a bubble-column reactor or a Stirred Tank reactor, And a gas phase and liquid phase double-looped bio-oil production system.

According to the present invention, in the vapor-phase and liquid-phase double circulation type biofuel producing system, when water is separated by gravity, a water layer having a high specific gravity forms a lower layer, And a cleaning liquid supply unit for supplying a cleaning liquid to the inside of the tank to clean the interior of the tank. The system includes a vapor-phase and liquid-phase double circulation type biofuel production system including a moisture stripping function for removing moisture in the tank.

According to the present invention, in the vapor-phase and liquid-phase double circulation type biofuel producing system, one or two or more of the moisture removing devices (13, 14) are connected in parallel and connected to the other side when one side is saturated, And a regenerator is connected to remove water from the bioreactor.

Comparative Example 1:

Fig. 1 shows a flow chart of a process for producing biofuel.

The crude oil stored in the raw material tank is mixed through a mixing process of mixing the crude oil with a catalyst for the desilverization and an accelerator and then subjected to a deoxidation reaction process to remove solid impurities from the reactor. The desorbed reactant reduces the acid value by removing the free fatty acid through the reaction under a low alcohol and a catalyst at 80 ° C or more. Thereafter, in order to remove water contained in the raw material and moisture generated by the reaction, the product is subjected to high-temperature vacuum dehydration and filtration through filtration to obtain the final product.

Fig. 2 shows a specific arrangement of apparatuses according to the flow chart of the biofuel oil production process. The raw material supplied from the raw material tank 16 through the motor is mixed with the catalyst and / or the promoter D in the mixer 7 and supplied to the main reactor 4, and the main reactor undergoes a desulfurization reaction. After the elimination reaction, a reaction product (E) containing a lower alcohol is fed to cause a deoxidation reaction while maintaining the reaction product at about 80 degrees Celsius or more. Since the lower alcohol is vaporized in a large amount at a high temperature of 80 ° C or higher, the deacidification reaction proceeds while passing through the condenser (8) while allowing the lower alcohol to be recycled and fed back to the main reactor. After completion of the deodorization and deoxidation reaction, the reaction mixture is allowed to stand for a certain period of time to induce layer separation of bio-heavy oil and water, and then the valve disposed at the bottom of the main reactor is opened to remove the water layer. The bio-heavy oil from which the water layer has been removed is transferred to and stored in the intermediate product tank 5, and the remaining water is separated through the vacuum distillation unit 6, and the final product is obtained through the filter.

In the conventional process, the supply tanks are one, so that raw materials including various acidity, moisture content and chemical components are mixed into one tank and then supplied to the main reactor. Therefore, Is inefficient to produce.

Also, in the conventional process, a chemical reaction is required to be carried out at a high temperature of 80 degrees Celsius or more to lower the acidity, so that a large amount of heat is required for the reaction, and a process cost and a device cost for liquefying the vaporized lower alcohol are required . Further, since a large amount of strong acid is required, an additional cost of wastewater treatment is required.

In addition, in the conventional process, it is necessary to leave a predetermined time after the deoxidation process to remove water. In order to remove moisture remaining in the biofuel, the intermediate product is stored in a storage tank and a decompression evaporator at a high temperature and a reduced pressure Since it is necessary to carry out a process of oil-water separation, a relatively large amount of time and cost are required.

Example 1:

Fig. 3 shows a manufacturing process flow chart in the present invention.

Two or more raw materials are stored in respective raw material tanks, and are classified and supplied in the respective raw material tanks, mixed using a blender, and catalyst and accelerator for desoldering are mixed together. Thereafter, the reactor is subjected to a deoxidation reaction process for removing solid impurities. The deoxidized reactant reduces the acid value by eliminating the free fatty acid through the esterification reaction under a low alcohol and a catalyst at 40 ° C. At the same time, the moisture removal is carried out simultaneously at room temperature and atmospheric pressure through a water removal device including a solid adsorbent And then filtered through a filtration process to obtain the final product.

Fig. 4 shows an example of a system for producing liquid and vapor double-looped bio-oil according to the present invention.

The raw material tank includes a first raw material tank 1 storing PAO (Palm Acid Oil), a second raw material tank 2 storing a CNSL (Cashew nut Shell Liquid), and a third raw material tank 2 storing BP (Bio-Pitch) 3); A mixer (7) in which a raw material supplied from the first, second and third raw material tanks and a catalyst for degumming are added and mixed; A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature; A reactor for esterifying free fatty acids with a portion of the liquid phase of the main reactor being circulated is characterized in that the esterification enzyme immobilized on the carrier is composed of a packed-bed type, and the inlet is provided with a lower alcohol for the esterification reaction An enzyme reaction reactor 12 for deoxidation, which comprises a component as a constituent; A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated;

A malodor removing unit (17) for removing volatile odor components in the dry air from which moisture has been removed through the water removal unit; And a base heat exchanger (20) for controlling the temperature of the dry air passing through the malodor remover (17) to assist in controlling the temperature of the main reactor, wherein the base heat exchanger (20) is disposed below the main reactor And a dry air supply device in which dry air from which odor components are removed is supplied for moisture stripping is disposed. Particularly, since the deoxidation enzyme reactor and the water removal device are operated at the same time, the moisture generated by the enzyme reaction is removed at the same time, so that the yield of the esterification reaction is at least 85%. As the water removal rate is increased, Can be reduced to 0.001% or less.

As a result of examining the above embodiments and comparative examples,

In the conventional process, the supply tanks are provided so that the raw materials including various acidity, moisture content and chemical components are mixed in one tank and then supplied to the main reactor. Therefore, It is inefficient to produce. In contrast, according to the present invention, it is possible to provide an economical feedstock supply system meeting the final specifications according to the acidity, moisture content, various chemical components, and the price of the raw material supplied by dividing the raw material supply tank into two or more.

Also, in the conventional process, a chemical reaction is required to be carried out at a high temperature of 80 degrees Celsius or more to lower the acidity, so that a large amount of heat is required for the reaction, and a process cost and a device cost for liquefying the vaporized lower alcohol are required . Further, since a large amount of strong acid is required, an additional cost of wastewater treatment is required. In contrast, the present invention introduces an enzyme reaction process capable of reacting even at low temperatures, and introduces an enzyme reaction unit such as esterase and lipase, which can be supplied at low cost, It is possible to achieve a high efficiency removal of the acid even in the case of maintaining the temperature of the condenser, so that no additional condenser is required and the use of a strong acid is not required, thereby reducing the equipment cost and the process cost.

In addition, in the conventional process, a step of allowing to stand for a predetermined time after the deoxidation process is required for removing moisture, and in order to remove moisture remaining in the biofuel, an intermediate product storage tank and an evaporator, Because it has to go through the process, time and cost are relatively high. On the other hand, in the present invention, by using a device for removing water at room temperature and normal pressure by using a water removal device including a solid type moisture adsorbent, facility cost and process cost can be remarkably reduced.

Particularly, since the deoxidation process and the water removal process are performed at the same time, the deoxidation rate and yield are remarkably increased.

 Properties of raw materials and physical properties and components of the final biofuel through comparative examples and examples

Item
Raw material


Quality standards

Bio fuel oil
PAO

CNSL
BIO
-PITCH Case 1 Case 2 Case 3
Flash point (℃)
190
116
10
70 or more
198
Kinematic viscosity (40 캜, mm 2 / s)
48 20 or more
~ 100 or less
23
Residual carbon content (% by weight)
below 10
One
Sulfur (weight%)
0.12
0.1 or less
Less than 0.1
Ash (weight%)
0.69
0.2
0.10 or less
0.01
Copper corrosion (50 ℃, 3h)
1b or less
1a
Pour Point (℃)
45
-30
27.5 or less
0
Density (15 캜, kg / m 3)
921
955
899
991 or less
916
Moisture (% by weight)
3
One
0.20 or less
0.12
0.02
0.02
Calculated value (mg KOH / g)
60
3
30
25 or less
17
12
2

alkali
(mg / kg)
Na
70 or less
6
Ca
30 or less
3
K
70 or less
9
Iodine (g / 100 g)
27.68
120 or less
108
Nitrogen (% by weight)
0.3 or less
Less than 0.1
Vanadium (mg / kg)
Less than 50
One
Calorific value (kcal / kg)
9,500
9,200
More than 9,000
9,480
9,530
9,599
Water and sediment (vol%)
3
2.2
0.5 or less
0.1
Silicon + aluminum + iron (mg / kg) 200 or less
37
Phosphorus (mg / kg)


Below 100
4

Case 1: Supply of raw materials is divided into three.

Case 2: The feedstock was divided into three feeds, and a water eliminator filled with a silica gel carrier was used to remove moisture.

Case 3: The feedstock was fed in three ways, and the water eliminator and enzyme reactor filled with silica gel carrier for water removal

As shown in the above table, raw materials supplied were three kinds such as PAO, CNSL and BIO-PITCH. In this case, the supply price of PAO is the lowest, but since the amount of water and the amount of water are high, it is necessary to efficiently control the amount of water and the amount of water to use the bio-oil channel. As a result of producing the biofuel by using the existing reaction process, the raw material tanks which are supplied firstly were separated into three kinds, and as a result, the specifications for supplying the biofuel were satisfied.

As a result of using the apparatus for circulating the air through the water eliminator filled with silica gel in order to reduce the amount of water and the computation cost and increase the calorific value, the amount of water was significantly reduced and the computational load was further reduced . It can be seen that the conversion rate is increased as the amount of water is decreased.

As a result of introducing an enzymatic reactor to reduce the computational cost, the conversion rate was further increased, and thus the calorific value was significantly increased.

Figure 5 shows the structure of a biofuel reactor.

The air dispersing device may be disposed at one side of the lower portion of the tank, or at the center of the tank, or may be disposed only at the outside of the tank, thereby inducing the specific gravity of the portion including the air to be lowered as the air is supplied. It is evident that it is possible to use the form of a bubble column reactor, a Stirred Tank reactor or various types of air-lift reactors in the form of conventional chemical reactors or microbial fermentors capable of supplying air from the bottom.

The bio-oil feedstock tank may be a reactor for esterification and metal-elimination reactions among the bio-heavy oil feedstocks, a storage tank for the bio-oil feedstock to which the reaction is completed, or a tank for storing raw materials before the reaction.

The moisture removing units 13 and 14 may include silica gel, silica blue, and / or zeolite in the moisture removing trap and the moisture removing trap, and the silica blue may be blue when dried and pink when the moisture is adsorbed. So that it is possible to know when to replace the solid type moisture removing agent in the water removal trap with the naked eye.

In addition, one or more of the water removal traps may be connected in parallel, and the water removal trap may be kit-replaceable so that the tank can be replaced if necessary, or the water removal trap can be replaced, As shown in FIG.

The replacement time of the water removal agent can be known by measuring the humidity of the air through the moisture removal trap with a humidity sensor.

The dry air that has passed through the moisture removal device may undergo a base heat exchange. The base heat exchange may be an auxiliary means for controlling the temperature of the tank. The tank itself may include base heat exchange. However, So that the reaction temperature inside the main reactor 4 can be controlled.

 The dry air that has undergone the heat exchange can be supplied to the bottom of the tank and distributed to the inside of the tank through the air disperser.

Since the end portion of the air disperser 19 is made of a porous material, the surface area of the bubbles can be increased by supplying fine air, thereby increasing the contact area with the fluid in the tank, thereby improving the water removal and temperature control effect.

The supplied dry air is brought into contact with the fluid in the tank to adsorb moisture, and then supplied to the water removal device through the condenser 8, and a humidity sensor is installed in the upper part of the main reactor 4, As a result, it is possible to determine whether the esterification reaction proceeds and / or the degree of moisture inside.

In the upper part of the tank, the substrate supplying part and the catalyst supplying part may be integrally or separately provided. In the case where water generated by the esterification reaction is generated in the lower part of the tank or is separated by gravity, water layer forms a lower layer and is provided with a reactant discharge unit for removing the reactant, and a washing liquid supply unit for supplying a washing liquid or the like to the inside is installed as needed.

One or two or more of the moisture removal traps may be connected in parallel, and the water removal trap may be kitted to be replaceable.

In addition, one or two or more of the water removal traps may be connected in parallel, and may include a supply part on the upper part and a discharge part on the lower part to replace the solid type moisture removing agent.

The water removal trap has a conical shape at its lower part and / or upper part, and is disposed to facilitate removal of the moisture removing agent from the lower part, and a mesh-type supporting membrane is provided at the lower part and / , So that the solid type moisture removing agent can be supported.

The solid type moisture removing agent may include silica blue, and may include a solid type moisture removal trap made of a transparent or semitransparent material, or a window formed to partially or wholly show a solid type moisture removing agent.

The moisture removal trap may be provided with a temperature control device for moisture adsorption and desorption.

1. First raw material tank
2. Second raw material tank
3. Third raw material tank
4. Primary reactor
5. semi-finished product tank
6. Evaporator
7. Mixer
8. Gas-liquid separation condenser
9. Gas-liquid separation condenser
10. Filter
11. Heat exchanger
12. Enzyme Reactor for Deoxidation
13, 14. Moisture removal device
15. Mixer
16. Material tank
17. Odor eliminator
18. Controller
19. Dry air supply (air disperser)
20. Heat exchanger

Claims (10)

(1) comprising a raw material tank (1, 2, 3), a mixer (7), a main reactor (4), an enzymatic reactor for deoxidation (12), a moisture removing device (13, A method for producing biofuel,
The raw material tank includes a first raw material tank 1 storing PAO (Palm Acid Oil), a second raw material tank 2 storing a CNSL (Cashew nut Shell Liquid), and a third raw material tank 2 storing BP (Bio-Pitch) 3);
A mixer (7) in which a raw material supplied from the first, second and third raw material tanks and a catalyst for degumming are added and mixed;
A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature;
A reactor for esterifying free fatty acids with a portion of the liquid phase of the main reactor being circulated is characterized in that the esterification enzyme immobilized on the carrier is composed of a packed-bed type, and the inlet is provided with a lower alcohol for the esterification reaction An enzyme reaction reactor 12 for deoxidation, which comprises a component as a constituent;
A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated;
A malodor removing unit (17) for removing volatile odor components in the dry air from which moisture has been removed through the water removal unit;
A heat exchanger (20) for controlling the temperature of the dry air through the odor remover (17) to assist in controlling the temperature of the main reactor;
And a dry air supplier disposed below the main reactor and supplying dry air from which odor components supplied from the malodor removing unit are removed is disposed, and the dry air discharged from the dry air supplier is subjected to moisture stripping A method of producing bio-heavy oil having a water content of 0.02 to 0.2% by weight, an acid value of 2 to 25, and a calorific value of 9,500 kcal / kg or more using a bio-heavy oil production system equipped with a heat exchanger,
(1) comprising a raw material tank (1, 2, 3), a mixer (7), a main reactor (4), an enzymatic reactor for deoxidation (12), a moisture removing device (13, A method for producing biofuel,
The raw material tank includes a first raw material tank 1 storing PAO (Palm Acid Oil), a second raw material tank 2 storing a CNSL (Cashew nut Shell Liquid), and a third raw material tank 2 storing BP (Bio-Pitch) 3);
A mixer (7) in which a raw material supplied from the first, second and third raw material tanks and a catalyst for degumming are added and mixed;
A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature;
And a deoxidation reactant supply unit for supplying a lower alcohol and an acid catalyst for the esterification reaction to the inlet for the esterification reaction of the free fatty acid as a part of the liquid phase of the main reactor is circulated;
A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated;
A malodor removing unit (17) for removing volatile odor components in the dry air from which moisture has been removed through the water removal unit;
A heat exchanger (20) for controlling the temperature of the dry air through the odor remover (17) to assist in controlling the temperature of the main reactor;
And a dry air supplier disposed below the main reactor and supplying dry air from which odor components supplied from the malodor removing unit are removed is disposed, and the dry air discharged from the dry air supplier is subjected to moisture stripping A method of producing bio-heavy oil having a water content of 0.02 to 0.2% by weight, an acid value of 2 to 25, and a calorific value of 9,500 kcal / kg or more using a bio-heavy oil production system equipped with a heat exchanger, (1) comprising a raw material tank (1, 2, 3), a mixer (7), a main reactor (4), an enzymatic reactor for deoxidation (12), a moisture removing device (13, A method for producing biofuel,
The raw material tank includes a first raw material tank 1 storing PAO (Palm Acid Oil), a second raw material tank 2 storing a CNSL (Cashew nut Shell Liquid), and a third raw material tank 2 storing BP (Bio-Pitch) 3);
A mixer (7) in which a raw material supplied from the first, second and third raw material tanks and a catalyst for degumming are added and mixed;
A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature;
A reactor for esterifying free fatty acids with a portion of the liquid phase of the main reactor being circulated is characterized in that the esterification enzyme immobilized on the carrier is composed of a packed-bed type, and the inlet is provided with a lower alcohol for the esterification reaction An enzyme reaction reactor 12 for deoxidation, which comprises a component as a constituent;
A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated;
A malodor removing unit (17) for removing volatile odor components in the dry air from which moisture has been removed through the water removal unit;
A heat exchanger (20) for controlling the temperature of the dry air through the odor remover (17) to assist in controlling the temperature of the main reactor;
And a dry air supplier disposed below the main reactor and supplied with dry air from which odor components removed from the odor eliminator are removed for moisture stripping,
A moisture sensor or a main reactor in contact with the gaseous phase of the main reactor and the raw material tanks, and a moisture activity measuring sensor in contact with the liquid phase of each raw material tank, and the supply of air supplied to the water removal device And the feed rate of the substrate supplied to the deoxidation reactor is controlled by controlling the feed rate of the feedstock fed to the deoxidation reactor or the feed rate of the feedstock fed to the deoxidation reactor. How to make Bio Heavy Oil (1) comprising a raw material tank (1, 2, 3), a mixer (7), a main reactor (4), an enzymatic reactor for deoxidation (12), a moisture removing device (13, A method for producing biofuel,
Wherein the raw material tanks each include two or more raw material tanks in which different raw materials are stored;
A mixer (7) in which two or more raw materials supplied from the two or more raw material tanks and a catalyst for degumming are added and mixed;
A main reactor (4) for performing a deactivation by reacting a mixed raw material supplied with a catalyst from the mixer at a predetermined temperature;
A reactor for esterifying free fatty acids with a portion of the liquid phase of the main reactor being circulated is characterized in that the esterification enzyme immobilized on the carrier is composed of a packed-bed type, and the inlet is provided with a lower alcohol for the esterification reaction An enzyme reaction reactor 12 for deoxidation, which comprises a component as a constituent;
A moisture removing device (13, 14) having a packed-bed type solid-state moisture adsorbent for removing water contained in the gas phase while a part of the gas phase of the main reactor is circulated;
A malodor removing unit (17) for removing volatile odor components in the dry air from which moisture has been removed through the water removal unit;
A heat exchanger (20) for controlling the temperature of the dry air through the odor remover (17) to assist in controlling the temperature of the main reactor;
And a dry air supplier disposed below the main reactor and supplied with dry air from which odor components removed from the odor eliminator are removed for moisture stripping,
A moisture sensor or a main reactor in contact with the gaseous phase of the main reactor and the raw material tanks, and a moisture activity measuring sensor in contact with the liquid phase of each raw material tank, and the supply of air supplied to the water removal device And the feed rate of the substrate supplied to the deoxidation reactor is controlled by controlling the feed rate of the feedstock fed to the deoxidation reactor or the feed rate of the feedstock fed to the deoxidation reactor. How to make Bio Heavy Oil 5. The method according to any one of claims 1 to 4,
Characterized in that an acidity sensor is provided on the liquid phase of the main reactor and each raw material tank and the circulation rate of the deoxidizing enzyme reactor or the feeding rate of the deoxidation reactant supply part is controlled according to the acidity of the main reactor, A method for producing biofuel using a heavy oil production system 5. The method according to any one of claims 1 to 4,
Wherein the solid-state moisture adsorbent includes silica blue, and the water removing apparatus includes a water removing device formed in a window or a transparent or semitransparent material so that the solid-state moisture adsorbent can be partially or wholly visible to the naked eye A method for manufacturing biofuel heavy oil using a biofuel production system equipped with a dry air heat exchanger 5. The method according to any one of claims 1 to 4,
The air distributor 19 is arranged at one side of the lower part of the tank or at the center or outside thereof so that the specific gravity of the part including air can be lowered as the air is supplied to induce the circulation inside the reactor A method for producing bio-heavy oil using a bio-heavy oil production system equipped with a dry air heat exchanger 5. The method according to any one of claims 1 to 4,
The main reactor is a type of air-lift reactor, a bubble-column reactor, or a Stirred Tank reactor. In order to remove water in the tank, a bio-heavy oil production system equipped with a dry air heat exchanger How to make 5. The method according to any one of claims 1 to 4,
When the moisture is separated by gravity, a reactant discharge portion for removing a high-specificity water layer from the lower layer to form a lower layer; And a cleaning liquid supply unit for supplying a cleaning liquid to the inside of the tank to clean the inside of the tank, and / or a cleaning liquid supply unit for supplying the cleaning liquid to clean the inside of the tank. Lt; / RTI >
5. The method according to any one of claims 1 to 4,
The dry air heat exchanger is equipped with one or more water removing devices (13, 14) connected in parallel, one side is connected to the other side, and one side is connected with a regenerating device to remove moisture by heating Of producing biofuel using biofuel production system

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