WO2022004267A1

WO2022004267A1 - Hydrocarbon manufacturing system using catalytic hydrogenolysis of oil/fat

Info

Publication number: WO2022004267A1
Application number: PCT/JP2021/021266
Authority: WO
Inventors: 慶一傳; 裕一郎東; 興哲松永
Original assignee: 株式会社レボインターナショナル
Priority date: 2020-06-29
Filing date: 2021-06-03
Publication date: 2022-01-06
Also published as: JPWO2022004267A1

Abstract

The present invention relates to a hydrocarbon manufacturing system that uses a catalytic hydrogenolysis reaction to manufacture a hydrocarbon from an oil/fat, said hydrocarbon manufacturing system comprising a processing device that performs the oil/fat catalytic hydrogenolysis reaction and in which an oil/fat supply line, a hydrogen gas supply line, and a water supply line are connected to a reaction part, said reaction part being provided with a carrier-equipped metal catalyst that is obtained by supporting a metal that has a hydrogenation capability on a neutral or weakly acidic metal oxide. A hydrocarbon that is obtained using the system or manufacturing method of the present invention can be used as a fuel corresponding to diesel fuel or a fuel corresponding to kerosene.

Description

Hydrocarbon production system by catalytic hydrocracking of fats and oils

The present invention relates to a method for producing lower and higher hydrocarbons obtained by catalytic hydrocracking and hydrogenation of oils and fats of biomass raw material oil, and an apparatus for producing the hydrocarbon.

Biomass-derived liquid fuel is desired from the viewpoint of being renewable and reducing the amount of carbon dioxide emitted by carbon neutrality.

Currently, fatty acid methyl ester has been put into practical use as a diesel fuel as a fuel using biomass as a raw material. However, in the fatty acid methyl ester, glycerin of about 10% of the fat and oil as a raw material is produced as a by-product in the step of methyl esterifying the fat and oil, and it is difficult to completely remove the glycerin and the fuel quality is deteriorated. Also, from the viewpoint of low temperature fluidity, fatty acid methyl ester has a problem because it has a high viscosity. In addition, fatty acid methyl ester has an unsaturated bond group in the carbon chain and has poor oxidative stability. In this way, fatty acid methyl esters leave a problem in quality. Therefore, there is a demand for biomass-derived hydrocarbons that correspond to petroleum-derived light oil and the like.

On the other hand, it is well known that the catalytic hydrocracking technology for hydrocarbons in petroleum is almost completed and has been put into practical use. According to Non-Patent Document 1, a catalyst in which a noble metal such as platinum is added to a zeolite-based solid acid catalyst is used as a decomposition catalyst, and naphtha, kerosene, light oil, etc. are produced by a reaction under high temperature and high pressure. There is. It is said that the addition of platinum to the catalyst suppresses carbon formation on the catalyst due to the lack of hydrogen in the above reactions with high-pressure hydrogen, and the catalyst life can be put to practical use. There are many technologies that basically follow this technology for biomass raw materials.

For example, in Non-Patent Document 2, the catalyst is nickel and molybdenum supported on strongly acidic silica-alumina, the raw material fat is jatropha oil, and an experiment is performed using a pressure-fixed bed type reactor (1 to 8 MPa). There is. The product is mainly limited to those having 15 to 17 carbon atoms as the carbon component of the raw material jatropha oil.

In addition, in the scattered literature, a catalyst in which a metal is supported on a solid acid of zeolite or silica-alumina is used to saturate unsaturated bond groups of fats and oils by hydrogenation to remove oxygen and decompose ester sites of fats and oils. It is a thing.

Development of liquid hydrocarbon fuel derived from biomass raw material The current situation is mainly for the purpose of fuel equivalent to light oil, but since demand for jet fuel equivalent to kerosene is expected in the future, hydrocarbon equivalent to light oil (15 carbon atoms). Not limited to ~ 20), low-intermediate hydrocarbons equivalent to kerosene (8 to 14 carbon atoms) must be taken into consideration. According to Non-Patent

Document

3, 1. 2. Manufacture Syngas by high-temperature gasification of Bymas and via Fisher Tropsch synthesis. 2. High-temperature thermal decomposition to produce crude oil and hydrogen treatment. 3. Alcohol is obtained from biomass by fermentation and then hydrogenated. There is hydrogen decomposition of fats and oils.

According to Patent Document 1, an example of hydrocracking of fats and oils using a catalyst prepared by special catalyst preparation is disclosed. The contents of the disclosure include "optimization of reaction conditions (temperature, LHSV (liquid space velocity), hydrogen supply amount, pressure of 1 MPa or less, etc.) and optimization of catalyst preparation (molybdenum addition / sulfurization treatment) to produce a product. Is made up of low-grade to high-grade hydrocarbons, and if fractionated, kerosene-equivalent products and light oil-equivalent products can be obtained separately. " However, the catalyst used is a solid acid zeolite on which a metal is supported, which is on the conventional route.

In general, all catalytic hydrocracking catalysts are composed of zeolite, a strongly acidic solid acid of silica-alumina, or a carrier having a strongly acidic catalytic function in which chloride is added to alumina, and a catalytic hydrocracking reaction. During the process, carbon precipitation occurs remarkably at the acidic points on the catalyst surface, leaving a problem with the life of the activity. As a countermeasure, high-pressure hydrogen is mainly used to prolong the catalyst life. Therefore, the current situation is that the development of a catalyst having an essentially longer catalyst life is desired.

WO2017 / 208497

Therefore, the subject of the present invention is a hydrocarbon production system that imparts catalyst stability, a hydrocarbon production method, and a hydrocarbon production system that imparts catalyst stability in order to produce hydrocarbons equivalent to light oil and kerosene by catalytic hydrocracking of fats and oils. It is to provide a hydrocarbon production apparatus.

As a result of diligent research to solve the above problems, the present inventors have made the fats and oils, which are the raw materials of various hydrogenated substances, a carrier having no acidic point, which is a cause of deterioration, or a carrier having a very small amount of acidic point. In the presence of a metal catalyst with a carrier carrying a metal having a hydrogenating ability, we have found a manufacturing system that realizes the addition of a hydrogenalytic decomposition function to the catalyst and the stabilization of the activity of the function in the presence of water. The invention was completed. Since the obtained hydrocarbon is equivalent to kerosene or light oil, it has excellent low-temperature fluidity and oxidative stability.

That is, the gist of the present invention relates to the following [1] to [7].
[1] A hydrocarbon production system that produces hydrocarbons from fats and oils by catalytic hydrocracking reaction.
A fat supply line, a hydrogen gas supply line, and a water supply line were connected to a reaction section provided with a metal catalyst with a carrier, in which a metal having a hydrocarbonizing ability was supported on a neutral or weakly acidic metal oxide. A hydrocarbon production system equipped with a processing device that performs a catalytic hydrogenation decomposition reaction of fats and oils.
[2] The hydrocarbon production system according to the above [1], wherein the hydrocarbon produced is a hydrocarbon having 5 to 20 carbon atoms.
[3] In the presence of a metal catalyst with a carrier
Hydrogen supply pressure is 0.2-5MPa,
The liquid space velocity of the supply liquid amount of fats and oils is set to 0.01 to 10.0 hr ^-1 .
The amount of water supplied to 100 parts by volume of fat and oil is 5 to 80 parts by volume, and the ratio of the flow rate of hydrogen to the flow rate of fat and oil is 50 to 1200 NL per liter of fat and oil, and the hydrogen, fat and water are used as the carrier. It is a method of producing a hydrocarbon having 5 to 20 carbon atoms by supplying it to a reaction section equipped with a metal catalyst and performing catalytic hydrocracking of fats and oils.
A production method in which the metal catalyst with a carrier is a catalyst composed of the following

groups

1 and 2.
Group 1: Catalysts with alumina, zirconia and / or titania as carriers.
Group 2: A catalyst in which at least one selected from the group consisting of ruthenium, nickel, platinum, palladium, iridium, rhodium, gold and silver is supported on alumina, zirconia and / or titania.
[4] The carrier of the metal catalyst with a carrier is alumina, the supported metal contains nickel and ruthenium, and the mass ratio of nickel to ruthenium is Ni: Ru = 10: 1 to 500: 1. ] The method described in.
[5] Oils include rapeseed oil, cottonseed oil, palm oil, coconut oil, sunflower oil, soybean oil, oil palm oil, coconut oil, jatrofa oil, olive oil, waste cooking oil, dark oil, animal oil oils and fats, algae oils and fats. The method according to the above [3] or [4], which is one or more selected from the group consisting of biomass dry distillate.
[6] A hydrocarbon produced by the method according to any one of [3] to [5] above, wherein the oil and fat is waste cooking oil and / or jatropha oil.
[7] A device for producing hydrocarbons by catalytic hydrocracking of fats and oils, from at least the fat and oil supply section, the hydrogen gas supply section, the water supply section, the reaction section, and the reaction product recovery section. Configured,
A hydrocarbon production apparatus in which a catalyst which is a neutral or weakly acidic metal oxide carrying a metal having a hydrogenating ability is present in the reaction unit.

According to the present invention, it is possible to provide an economically advantageous method for producing a desired hydrocarbon by carrying out a catalytic hydrogenation decomposition reaction of fats and oils according to the formulation of the present invention. Hydrocarbons (fuels equivalent to kerosene and / or light oil) can be produced by such a method.

FIG. 1 is a diagram showing a manufacturing system and a manufacturing apparatus. FIG. 2 is a diagram showing the stability and durability of the catalyst. FIG. 3 is a diagram showing decomposition of an ester moiety and cleavage of a carbon chain. In FIG. 3, the selection rate as an evaluation when divided into kerosene equivalent and light oil equivalent is shown. That is, _{among the produced C 5-20} hydrocarbons (HC), _{the selectivity of C 8-14} HC as equivalent to kerosene was shown.

There is also the idea of applying the petroleum raw material technology to various fats and oils in the field of the present invention as it is, but the use of solid acids in catalysts of expensive components such as zeolite and platinum, and the precipitation of carbon in solid acids are unavoidable. Therefore, in order to stabilize the catalyst, a regeneration device that oxidizes and removes the precipitated carbon must be installed in the process. When targeting biomass raw materials, locally produced and locally consumed fuel production equipment is often important, which poses a major problem for economic acceptance.

1. 1. Hydrocarbon Production System The present invention proposes a hydrocarbon production system without a regeneration facility for catalyst activation and stabilization. Specifically, the following system can be mentioned.
A hydrocarbon production system that produces hydrocarbons from fats and oils by catalytic hydrocracking reaction.
A fat supply line, a hydrogen gas supply line, and a water supply line were connected to a reaction section provided with a metal catalyst with a carrier in which a metal having a hydrocarbonizing ability was supported on a neutral or weakly acidic metal oxide. , A hydrocarbon production system equipped with a processing device that performs a catalytic hydrogenation decomposition reaction of fats and oils.

By connecting a water supply line and the presence of water during the reaction, hydrocracking proceeds even in a metal catalyst with a carrier that does not use a solid acid, and the catalyst life can be further extended. Is.
The hydrocarbon produced by this system is preferably a hydrocarbon having 5 to 20 carbon atoms, and more preferably a hydrocarbon having 8 to 20 carbon atoms.

2. 2. Hydrocarbon Production Method The hydrocarbon production method of the present invention is carried out in the presence of a metal catalyst with a carrier.
Hydrogen supply pressure is 0.2-5MPa,
The liquid space velocity of the supply liquid amount of fats and oils is set to 0.01 to 10.0 hr ^-1 .
The amount of water supplied to 100 parts by volume of fat and oil is 5 to 80 parts by volume, and the ratio of the flow rate of hydrogen to the flow rate of fat and oil is 50 to 1200 NL per liter of fat and oil, and the hydrogen, fat and water are used as the carrier. It is a method of producing a hydrocarbon having 5 to 20 carbon atoms by supplying it to a reaction section equipped with a metal catalyst and performing catalytic hydrocracking of fats and oils.
The metal catalyst with a carrier is a production method in which the catalyst is composed of the following

groups

1 and 2.
Group 1: Catalysts with alumina, zirconia and / or titania as carriers.
Group 2: A catalyst in which at least one selected from the group consisting of ruthenium, nickel, platinum, palladium, iridium, rhodium, gold and silver is supported on alumina, zirconia and / or titania.

The fats and oils in the present invention are selected from, but not limited to, rapeseed oil, cottonseed oil, palm oil, coconut oil, sunflower oil, soybean oil, rice oil, oil palm oil, coconut oil, jatrofa oil, and olive oil. It is preferable that the amount is one or more. Further, fats and oils from algae and animal oils are also preferable. Further, the used waste cooking oil of tempura oil is more preferable at present. Dark oils from the fat processing process, as well as animal oils, are also available. In addition, it can also be applied to biomass carbonization oil.

An example of the reaction operation in the production of hydrocarbon will be described.
The hydrogen supply pressure during the treatment varies depending on the reaction requirements for obtaining the desired product and the accompanying measures for prolonging the catalyst life (suppressing carbon precipitation), but generally becomes the following hydrogen reaction pressure. It is 0.2 to 5.0 MPa, preferably 0.2 to 3.0 MPa, and more preferably 0.5 to 1.5 MPa.

Set the flow rate of raw material fats and oils to a predetermined value. Specifically, the flow rate of the fat and oil is set to a liquid space velocity of 0.01 to 10.0 hr ^{-1 based} on the fat and oil. It is preferably 0.05 to 5.0 hr ^-1 , and more preferably 0.05 to 3.0 hr ^-1 . In the present invention, the lower the liquid space velocity, the more advantageous the reaction tends to be, but if it is less than the above lower limit, a reactor having an extremely large internal volume tends to be required, and an excessive capital investment tends to be required. On the other hand, when the liquid space velocity exceeds the above upper limit value, the reaction tends not to proceed sufficiently.
From the viewpoint of preheating efficiency and reaction efficiency, the temperature at the inlet of the reaction section when supplying fats and oils is preferably 25 to 250 ° C, preferably 100 to 200 ° C, and even more preferably 150 to 180 ° C.

In the present invention, it is important to supply a predetermined amount of water to fats and oils under predetermined reaction conditions. The flow rate of the supplied water is preferably set to 5 to 80 parts by volume, more preferably 10 to 60 parts by volume, and further preferably 20 to 50 parts by volume with respect to 100 parts by volume of fat and oil. If it is 5 or less, the effect of adding water is unlikely to appear, and if it exceeds 80, it is disadvantageous in terms of calorific value. The temperature at the inlet of the reaction part at the time of water supply is preferably 20 to 250 ° C. from the viewpoint of preheating efficiency and reaction efficiency. , 100 to 200 ° C, more preferably 150 to 180 ° C. The oil / fat supply temperature is preferably within ± 20 ° C, more preferably within ± 10 ° C, and even more preferably within ± 5 ° C.

The ratio of the hydrogen flow rate to the flow rate of fats and oils is set to 50 to 1200 NL (normal liter) of hydrogen per 1 L of fats and oils. Preferably, hydrogen is 200 to 1000 NL per 1 L of fat and oil. More preferably, it is 300 to 800 NL. When the ratio of hydrogen to fats and oils is less than the above lower limit, the reactivity tends to decrease or the activity tends to decrease rapidly. On the other hand, if the ratio exceeds the above upper limit, excessive capital investment such as hydrogen supply equipment tends to be required.

The reaction temperature is preferably 250 ° C to 500 ° C, more preferably 300 ° C to 450 ° C, and even more preferably 330 ° C to 400 ° C. At 250 ° C or lower, the reaction rate decreases, and at 500 ° C or higher, dehydrogenation or the like occurs and carbon precipitation is likely to occur.

The metal catalyst with a carrier is preferably filled in a reactor such as a known reaction tube.
As the type of reactor, a fixed bed method can be adopted. Hydrogen can adopt either a countercurrent or parallel flow form with respect to fats and oils. In addition, a plurality of reactors may be used to combine countercurrent and parallel current. The general format is downflow, and a gas-liquid double parallel flow format can be adopted. Further, the reactor may be used alone or in combination of two or more, and a structure in which the inside of one reactor is divided into a plurality of catalyst beds may be adopted.

The main component of the hydrocarbon produced by the production method of the present invention is one having 5 to 20 carbon atoms.

3. 3. Hydrocarbon production system Action mechanism According to the conventional knowledge, the triglyceride moiety of fats and oils is decomposed by a decarbonation reaction and a hydrogenation dehydration reaction under hydrogen gas with a hydrogenation decomposition metal catalyst. The reactions required for fuel reforming into gasoline, kerosene and gas oil, such as petroleum-derived carbon chain cleavage, cyclization dehydrogenation, dehydrogenation and isomerization reactions, are triggered by the Bronsted acid sites of solid acids. It is said to be promoted by Calvenim ion.

In the conventional concept, a dual catalyst is used in which a solid acid as a decomposition catalyst is used as a carrier and a metal catalyst such as a noble metal is added. That is, it is interpreted that hydrogenation decomposition, carbon chain cleavage, isomerization and cyclization isomerization by an acid catalyst are carried out, and hydrogenation and dehydrogenation by a metal catalyst are carried out.

On the other hand, the acid point of the solid acid is estimated as the place where carbon precipitation occurs. Therefore, in the catalyst of the present invention, a neutral carrier such as alumina is used while avoiding the use of solid acid. A weakly acidic carrier with a trace amount of acidity may be used.

In the present invention, hydrogen is dissociated adsorbed on the carrier with a metal catalyst, oxonium ions by a coordination bond with the added water (H 3 _O) ⁺ next (Non-Patent Document 4), moving the solid acid on the surface of the carrier Used in place of the acid point of. That is, when the water is adsorbed on the surface of the metal catalyst, it becomes an oxonium ion, and an active proton is generated and moves on the surface of the carrier to have the same reactivity as the Bronsted acid point of a solid acid. The oxonium ion is classified as a strong acid and has pKa≈-2 as compared with pKa≈-3 to -5 of sulfuric acid, and therefore has an acid strength equivalent to that of the Bronsted acid point of a solid acid. That is, since it is equivalent to the acid point of a solid acid, it can be presumed that the carbon chain is converted into carbenium ion by the oxonium ion and the cleavage of the carbon chain proceeds in a chain reaction. That is, the oxonium ion has a hydrogenation resolution similar to that of the acid point of a solid acid, and can be applied to cleavage of a carbon chain of a general hydrocarbon, cyclization dehydrogenation reaction, dehydrogenation reaction, isomerization reaction and the like.

By the way, in the hydrogenation deoxidation of the ester site and the hydrogenation reaction of the unsaturated part, the substrate (ester part and unsaturated part) needs to be adsorbed on the solid surface, but it is easily adsorbed on the acidic point. Even with a neutral carrier, the substrate is adsorbed on the oxonium ions on the surface, and the atomized hydrogen spilled over from the metal surface promotes hydrogenation deoxidation and hydrogenation reaction at the ester moiety.

Slightly generated water generated at the beginning of the reaction process showed acidity without addition of water, and the reaction proceeded slightly, followed by acceleration of the produced water effect and catalytic action. However, the amount of produced water is at most about 10 parts with respect to fats and oils, and its catalytic effect is not sufficient.

Oxonium ions have a large hydrogen donating effect and have a carbon-suppressing effect and do not cause carbon precipitation by themselves, but if the amount is small, carbon precipitation at the adsorption point of the substrate cannot be completely suppressed and the catalytic action deteriorates over time. .. Therefore, a sufficient amount of oxonium ion is required, and therefore a necessary and sufficient amount of added water is required. In addition, a trace amount of aromatic compound may be produced as a by-product. When the reaction is carried out at a relatively low pressure, this aromatic compound may be adsorbed on the catalyst carrier and cause carbon precipitation. For the purpose of preventing such adsorption, it is effective and preferable to add 0.1 to 5% by mass of sodium hydroxide or ammonia to the added water.

4. Form of Metal Catalyst with Carrier In the present invention, it is a catalyst in which a metal having a function of dissociating hydrogen to generate atomic hydrogen and a hydride ability is supported on a neutral or weakly acidic porous metal oxide. The metal is one or more selected from the group consisting of ruthenium, nickel, platinum, palladium, iridium, rhodium, gold, and silver, and the porous metal oxide of the carrier is composed of alumina, zirconia, and titania. One or more of the more selected are metal catalysts with carriers.

When it is possible to suppress carbon precipitation to a certain extent by the effect of hydrogen at a relatively high pressure, it is also possible to disperse and fix zeolite or silica powder on the porous metal oxide of the carrier to impart acidity in the production system of the present invention. It is the scope of application.

A preferable combination of the carrier in the metal catalyst with a carrier and the metal to be supported is, for example, a combination in which the carrier is alumina and the metal contains nickel and ruthenium. In this case, the mass ratio of nickel to ruthenium (Ni: Ru) is preferably 10: 1 to 500: 1, more preferably 20: 1 to 250: 1, and even more preferably 100: 1 to 140: 1.

The particle size is preferably 0.01 to 3.0 mm, more preferably 0.03 to 3.0 mm. If the particle size is smaller than 0.01 mm, the pressure loss of the catalyst layer becomes excessive, which is not preferable. Further, when the particle size is larger than 3 mm, a space is created between the catalysts so that fats and oils can pass through. However, since the surface area per unit volume is small due to the large particles, the contact efficiency tends to deteriorate, which is not preferable. In terms of handling (handling) of catalyst particles, those having a particle diameter of 0.5 to 3 mm are more preferably adopted.
Practically, a catalyst having a diameter of 1 mm to 3 mm is recommended.

Before using this catalyst, it is preferable to calcin it in the air to reduce hydrogen.
In order to oxidize and remove impurities mixed in the catalyst preparation, it is preferable to bake at 300 to 450 ° C. in air, more preferably 350 to 400 ° C. The heat treatment time in the air is preferably 1 to 5 hours.
It is important to reduce what is oxidized during the firing process. The heat treatment time in hydrogen gas is preferably 1 to 5 hours, preferably 350 ° C. to 450 ° C.

5. Hydrocarbons and Hydrocarbon Production Equipment The hydrocarbon of the present invention is characterized by being produced by the method for producing a hydrocarbon of the present invention. The obtained hydrocarbon is a mixture of hydrocarbons corresponding to light oil or kerosene from the viewpoint of boiling point and carbon number.

The hydrocarbon production apparatus of the present invention is an apparatus for producing hydrocarbons by catalytic hydrogenation and decomposition of fats and oils, and is at least an oil / fat supply unit, a hydrogen gas supply unit, a water supply unit, a reaction unit, and a reaction unit. It is composed of a reaction product recovery unit, preferably further provided with means for adjusting the flow rate of fats and oils, the flow rate of added water, and the flow rate of hydrogen gas. There are catalysts that are weakly acidic metal oxides. In the reaction section, the supplied oil and fat and the supplied hydrogen gas are reacted by adding water in the presence of a metal catalyst with a carrier. By supplying hydrogen, fats and oils and water to a reaction section provided with a metal catalyst with a carrier, the fats and oils are catalytically hydrolyzed to produce a hydrocarbon having 5 to 20 carbon atoms. Further, it is preferable that the hydrocarbon production apparatus of the present invention is further equipped with a hydrogen gas production apparatus, a product separation apparatus for distilling and separating the reaction termination product, and the like, if necessary.

Hereinafter, the hydrocarbon production apparatus of the present invention will be described more specifically with reference to FIG.
The manufacturing apparatus of the present invention is composed of at least three parts: (1) water, oil and fat and hydrogen gas supply part, (2) reaction part and (3) reaction product recovery part. That is, in the manufacturing apparatus exemplified in FIG. 1, fats and oils and water are simultaneously supplied to the reaction section. In the water, fat and hydrogen gas supply section of (1), fat and oil are sent from line 1 to the upper part of the reaction tube 7 through the liquid supply pump 2, and hydrogen is sent from line 3 through the hydrogen gas flow rate control unit 4 to the upper part of the reaction tube 7 (preferably. Is supplied downstream of the oil supply point). The added water is supplied from the water supply unit, that is, the line 13 through the added water supply pump 14. That is, fats and oils and water are mixed and supplied to the reaction section immediately before the entrance of the reaction section. In the reaction section of (2), in the reaction tube 7 in which the thermometer 5 is installed in the center of the inside, heating and temperature control are performed in the electric heating furnace 8 equipped with the thermometer 6. In the reaction product recovery unit (3), the gas-liquid mixture discharged from the lower part of the reaction tube 7 is cooled by the condenser 9 and then guided to the gas-liquid separation device 10. Moisture is recovered by the condensate receiver 11. The produced hydrocarbons and unreacted substances are stored in the condensate receiver 12 having a cooling function. Unreacted hydrogen gas and gaseous hydrocarbons are discharged from the condensate receiver 12 (the gaseous hydrocarbons are separated from the hydrogen gas by another device and used as fuel or the like). The contents of the condensate receiver 12 are separated into hydrocarbons equivalent to light oil or kerosene and unreacted substances (high boiling point substances) by another distillation apparatus.

In the present invention, fats and oils, water and hydrogen need to coexist in the reaction section. These three components may be connected to the reaction section via different lines, or as shown in FIG. 1, the fats and oils are supplied so that the fats and oils and water are mixed immediately before the entrance of the reaction section. After the line to supply water and the line to supply water are connected, they may be connected to the reaction section.

A metal catalyst with a carrier exists in the reaction section of the hydrocarbon production apparatus of the present invention. With such a catalyst, hydrogen gas and water can be supplied to produce a hydrocarbon equivalent to light oil or kerosene.

The hydrogen gas production apparatus is, for example, a steam reforming reaction apparatus (for example, a steam reforming reaction apparatus provided with a recycling raw material supply unit for a low boiling gas substance separated from a product in the hydrocarbon production apparatus of the present invention, or a city gas supply unit. , Equipment with a ruthenium-alumina catalyst).

As the product separation device for performing product separation, for example, a normal pressure or vacuum distillation column can be adopted. Low boiling gaseous substances are recycled to hydrogen gas production equipment. Further, if a large amount of gas oil equivalent is desired, it is recommended that the light oil equivalent be recycled and supplied to the catalytic hydrocracking apparatus to be converted into kerosene equivalent.

The product separation device, that is, the high boiling point discharged from the lower part of the distillation column, may be recovered as combustion fuel and supplied to the combustion / energy recovery device for use as a heat source required for the entire device.

Hereinafter, the present invention will be described in more detail based on Examples and the like, but the present invention is not limited to such Examples.

[Catalyst preparation]

Pretreatment of Alumina Prepared by adding purified water to 1 mol / L of nitric acid (60%) manufactured by Nacalai Tesque. 1 mol / L nitric acid 50 cc was mixed with 50 cc activated alumina and mixed in a 200 ml eggplant flask. The mixture was stirred for 4 hours using a rotary evaporator. After that, nitric acid-treated activated alumina was filtered, and washing and filtration were repeated 3 times with 50cc purified water. The catalyst carrier was a dryer set at 103 ° C. and dried for 3 hours to remove moisture.

Supporting metal A conventional impregnation method using 10 parts by mass of Ni and 0.1 part by mass of Ru (10.1 parts by mass in total) with respect to 100 parts by mass of activated alumina pretreated with nitrate in this way. Prepared a metal catalyst with a carrier.

Activated alumina: Union Showa Co., Ltd., D-201 5 × 8 particle size 3 mm
Nickel Nitrate (Nickel Nitrate (II) Hexahydrate, manufactured by Wako Pure Chemical Industries, Ltd.)
Ruthenium nitrate

The following treatment was performed for each experiment.
Air firing: 400 ° C 4hr
Hydrogen reduction: 350 ° C 4hr

[Hydrocarbon production equipment]
As a hydrocarbon production apparatus, a fixed-bed flow reactor having a normal pressure as shown in FIG. 1 was used, a catalyst (50 cc) was filled inside the reaction tube 7, and a catalytic hydrocracking reaction of fats and oils was carried out. As the reactor, a reaction tube 7 having an inner diameter of 10.22 mm and a catalyst filling length of 291 mm was used, and a thermocouple was mainly installed in the catalyst layer, and the temperature of the catalyst layer was actually measured.

The temperature of the reactor was controlled by the electric heating furnace 8, and the reaction product was cooled by a room temperature water cooler, and then the condensed components were separated. Gas crotography analysis of the liquid component recovered in the condensate receiver (hydrocarbon) 12 was performed. The hydrogen flow rate was controlled by the flow rate control valve. Oils and fats as raw material oil and added water were supplied by a quantitative liquid pump.

Examples and Comparative Examples [Reaction conditions]
Ingredients: Waste cooking oil owned by Revo International Co., Ltd. (used tempura oil)
Catalyst: Activated alumina 3 mmφ carrier, Ni 10% by mass, Ru 0.1% by mass
Reaction temperature: 350 ° C,
Operation method: 32 hours continuous operation Waste cooking oil supply amount: 0.11 mL / minute Hydrogen (gas) supply pressure: 0.8 MPa gauge pressure Hydrogen supply amount 86.7 NmL / min LHSV = 0.13 (oil and fat supply amount L) / Hr / catalyst L)
Oil and fat temperature at the time of supply = 25 ° C
Water temperature at supply = 20 ° C
The amount of added water is as shown in Table 1.

[Reaction result]
Table 2 shows the activity evaluations of Examples and Comparative Examples.
HC (hydrocarbon) yield: An index of the decomposition rate of the ester moiety. _{C 5-20} was measured by gas chromatography.
Relative density (25 ° C): Deoxidation of the ester site reduces the specific density.

[Evaluation of manufacturing system]
From Table 2 and FIGS. 2 to 3, it can be seen that the activity is clearly improved and stabilized by adding the added water and increasing the added water.
Activity: Since the ester site was decomposed into hydrocarbons and kerosene-equivalent components were observed, low-to-intermediate hydrocarbons were produced and the cleavage function was confirmed.
Improvement of activity: It was clearly confirmed that the activity was improved as the added water increased.
Stability of activity: It was confirmed that the initial activity of the catalyst can be maintained even after the lapse of 32 hours when the amount of added water is large.

The hydrocarbon obtained by the system or manufacturing method of the present invention can be used as a fuel equivalent to light oil or a fuel equivalent to kerosene.

1 line 2 oil supply pump 3 line 4 hydrogen gas flow rate control unit 5 thermometer 6 thermometer 7 reaction tube 8 electric heating furnace 9 condenser 10 gas-liquid separator (moisture separator)
11 Condensation receiver (moisture)
12 Condensation receiver (hydrocarbon)
13 Line 14 Additive water supply pump

Claims

A hydrocarbon production system that produces hydrocarbons from fats and oils by catalytic hydrocracking reaction.
A fat supply line, a hydrogen gas supply line, and a water supply line were connected to a reaction section provided with a metal catalyst with a carrier, in which a metal having a hydrocarbonizing ability was supported on a neutral or weakly acidic metal oxide. A hydrocarbon production system equipped with a processing device that performs a catalytic hydrogenation decomposition reaction of fats and oils.
The hydrocarbon production system according to claim 1, wherein the hydrocarbon produced is a hydrocarbon having 5 to 20 carbon atoms.
In the presence of a metal catalyst with a carrier
Hydrogen supply pressure is 0.2-5MPa,
The liquid space velocity of the supply liquid amount of fats and oils is set to 0.01 to 10.0 hr -1 .
The amount of water supplied to 100 parts by volume of fat and oil is 5 to 80 parts by volume, and the ratio of the flow rate of hydrogen to the flow rate of fat and oil is 50 to 1200 NL per liter of fat and oil, and the hydrogen, fat and water are used as the carrier. It is a method of producing a hydrocarbon having 5 to 20 carbon atoms by supplying it to a reaction section equipped with a metal catalyst and performing catalytic hydrocracking of fats and oils.
A production method in which the metal catalyst with a carrier is a catalyst composed of the following groups 1 and 2.
Group 1: Catalysts with alumina, zirconia and / or titania as carriers.
Group 2: A catalyst in which at least one selected from the group consisting of ruthenium, nickel, platinum, palladium, iridium, rhodium, gold and silver is supported on alumina, zirconia and / or titania.
The third aspect of claim 3, wherein the carrier of the metal catalyst with a carrier is alumina, the supported metal contains nickel and ruthenium, and the mass ratio of nickel to ruthenium is Ni: Ru = 10: 1 to 500: 1. Method.
Fats and oils are rapeseed oil, cottonseed oil, palm oil, coconut oil, sunflower oil, soybean oil, oil palm oil, coconut oil, jatrofa oil, olive oil, waste cooking oil, dark oil, animal oil fats and oils, algae fats and oils, and biomass dry distillate oil. The method according to claim 3 or 4, wherein the method is one or more selected from the group consisting of.
A hydrocarbon produced by the method according to any one of claims 3 to 5, wherein the oil and fat is waste cooking oil and / or jatropha oil.
It is a device for producing hydrocarbons by catalytic hydrogenation and decomposition of fats and oils, and is composed of at least a fats and oils supply unit, a hydrogen gas supply unit, a water supply unit, a reaction unit, and a reaction product recovery unit.
A hydrocarbon production apparatus in which a catalyst which is a neutral or weakly acidic metal oxide carrying a metal having a hydrogenating ability is present in the reaction unit.