JP2012219141A - Diesel fuel manufacturing reactor, and diesel fuel manufacturing system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a diesel fuel manufacturing reactor capable of obtaining cracked petroleum in a higher yield in the catalytic cracking reaction to prepare cracked petroleum from stock oil and a diesel fuel manufacturing system capable of obtaining diesel oil in a higher yield.SOLUTION: A heating means (first heating section H1) is provided around reaction tank 1 and second heating section H2 is also provided in the inside of catalyst layer 2, and above the catalyst layer 2, an injection section 3a is provided to widely inject stock oil introduced from introduction section 3. Around the catalyst layer 2, a gas-liquid flowable plate section (plates A to C) is installed and a partition between the catalyst layer 2 and a space section (first to fourth spaces S1 to S4) having a predetermined volume is formed and part of a regeneration gas is supplied to the catalyst layer 2 through the space section.

Description

  The present invention relates to a diesel fuel production reactor for producing diesel fuel using a catalyst and a diesel fuel production system using the same. In particular, as a raw material for producing diesel fuel, a reactor for producing diesel fuel using a catalytic cracking method capable of using waste cooking oil, vegetable oil, animal oil, various mineral oils alone or in combination, and The present invention relates to a diesel fuel production system used.

  Diesel fuel oil has been produced mainly by the process of reforming, desulfurization, denitrogenation, etc. as necessary from the product of catalytic cracking or pyrolysis of petroleum gas oil fraction or residual oil. It had been. On the other hand, the use of waste cooking oil, vegetable oils, animal fats and various mineral oils as a raw material for producing diesel fuel has been studied and put into practical use from the viewpoint of securing raw materials to replace petroleum. For example, a configuration as shown in FIG. 6 (A) has been proposed because the conventional technology for producing diesel fuel from waste cooking oil could not be applied. For example, see Patent Document 1). Pre-treatment unit 101 that removes solid substances from waste cooking oil, dehydration and deodorization unit 102 that heats waste cooking oil to evaporate and remove moisture and odorous substances from waste cooking oil, and contains a catalyst by dissolving an alkaline substance in alcohol A catalyst-containing alcohol solution preparation unit 103 that prepares an alcohol solution, a mixed reaction unit 104 that mixes and stirs waste cooking oil and a catalyst-containing alcohol solution to obtain a reaction product, and separates the reaction product into a light liquid and a heavy liquid Liquid-liquid separation unit 105, purification unit 106 that mixes light liquid with solid adsorbent to adsorb impurities in the light liquid onto the solid adsorbent, and separates and removes solid adsorbent adsorbing impurities from the light liquid The solid-liquid separation part 107 and the neutralization process part 108 which neutralizes the catalyst which consists of an alkaline substance in a heavy liquid by mixing a heavy liquid with a neutralizing agent are provided.

  Here, as shown in FIG. 6B, the mixing reaction unit 104 includes a stirring reaction tank 160 equipped with a catalyst-containing alcohol solution metering pump 156, a dewatered and deodorized waste cooking oil metering pump 158, and a multistage blade 162. It is composed of The stirring reaction tank 160 has a multistage blade 162 attached to a rotating shaft 164 installed at the center of a cylindrical vessel, and the rotating shaft 164 is rotated by a drive motor 166 so that the stirring reaction tank 160 can be rotated from the bottom. The dehydrated / deodorized waste cooking oil flowing upward and the catalyst-containing alcohol solution are continuously mixed, and the waste cooking oil and alcohol are reacted. Two agitation reaction tanks 160 are installed in a cascade manner, and waste cooking oil sent from the dehydration / deodorization unit 102 and catalyst-containing alcohol solution sent from the catalyst-containing alcohol solution tank 154 are respectively sent by metering pumps 158 and 156. After being continuously introduced into the bottom of the first stirring reaction tank 160 at a constant rate, after passing through the inside of the stirring reaction tank 160, it flows out from the outlet of the first stirring reaction tank 160, and further the second stirring reaction tank 160 After being introduced into the bottom of the reaction tank 160 and passing through the inside of the stirred reaction tank 160, it flows out from the outlet of the second stirred reaction tank 160 (see Patent Document 1, paragraph 0030, FIG. 3).

  In addition, as a light oil alternative fuel technology using fats and oils such as waste cooking oil, a transesterification method (FAME) has been put into practical use and widely adopted (for example, see Patent Document 2), and a hydrogenation method (for example, Patent Document) as another method 3), fluidized bed catalytic cracking (FCC) method (for example, see Patent Document 4), and the like.

Japanese Patent Laid-Open No. 10-231497 JP 2008-1856 A JP 2007-153928 A JP 2007-177193 A

However, the light oil alternative fuel technology or the diesel fuel production apparatus as described above sometimes has the following problems and problems.
(I) In general, in the fixed-bed catalytic cracking method, the catalyst near the heating part (heating tube, heater, etc.) in the reactor is at a high temperature at which the reaction easily proceeds, so that the coke is deposited. Due to the relatively large amount, the regeneration air flow path is biased in the regeneration process, and the catalyst cannot be sufficiently regenerated, and if the reaction and regeneration are repeated as it is, coke lumps are produced and the catalyst function is impaired, Causes heat transfer inhibition (once a lump is formed, the burning rate becomes extremely slow, making it virtually impossible to regenerate). Furthermore, on the catalyst on which coke is deposited, the target reaction rate is remarkably reduced, and free fatty acids other than light oil and hydrocarbons having a small number of carbons are by-produced, resulting in a problem that the quality is lowered.
(Ii) Further, in response to the problem in the fixed bed system, a method in which the catalyst moves between the reactor and the regenerator and the coke quickly burns and removes by adopting the circulating fluidized bed system. At this time, because it is a fluidized bed, the amount of coke removed and the regeneration temperature are uniform, but the equipment is large and ancillary equipment is required, so it is not suitable for small-scale technology such as biodiesel fuel production. It is. In addition, the structure of the reactor and the regenerator is complicated, and it is not suitable for small-scale facilities in terms of heat balance. Furthermore, there has been a problem that it is necessary to replenish the catalyst and discard the catalyst powder due to loss of catalyst wear.
(Iii) In the production method as shown in FIG. 6 (A), the stirring blade in the reactor for stirring the catalyst as shown in FIG. 6 (B) is indispensable. And coke agglomeration can be suppressed, but catalyst wear and pulverization due to contact between the stirring blades and the catalyst and contact between the catalysts becomes unavoidable, resulting in problems of catalyst replenishment and catalyst powder extraction.
(Iv) In addition, the transesterification method has a slow reaction rate, requires petroleum-derived methanol, and has problems such as treatment of glycerin, which is a by-product, and wastewater treatment that occurs in the water washing step. Although the hydrogenation method has a high reaction rate and high quality as a light oil, it requires a hydrogen source and high-pressure gas equipment. Further, water is generated as a by-product, and the synthetic oil is paraffin. There are problems such as inferiority.

  Therefore, the present invention has been made in view of the above problems, and in a catalytic cracking reaction for producing cracked oil from raw oil, coke generated with the reaction can be quickly removed so that high catalyst efficiency can be maintained. , A reactor capable of uniformly and efficiently regenerating the packed catalyst to obtain a higher yield of cracked oil, and a diesel fuel production to obtain a higher yield of diesel fuel The purpose is to provide a system.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by the following diesel fuel production reactor and a diesel fuel production system using the same, and have completed the present invention.

The present invention comprises a reaction tank having a catalyst layer filled with a solid catalyst, and in a reactor for producing cracked oil composed of hydrocarbons from raw material oil by a catalytic cracking method,
A heating unit comprising a first heating unit provided around the reaction tank, a second heating unit provided in the catalyst layer, and at least a plate A provided in a circulating part of the catalyst layer, the catalyst A plate part through which gas and liquid can flow, comprising a plate B provided in the lower part of the layer, a plate C provided around the second heating part, a first space provided in the upper part of the catalyst layer, A second space provided between the plate A and the inner surface of the reaction vessel; a third space provided between the plate B and the inner surface of the reaction vessel; and the plate C and the second heating unit. A space portion having a predetermined volume each comprising a fourth space provided therebetween, and a catalyst regeneration processing portion comprising a regeneration gas introduction portion and a gas discharge portion provided in the reaction tank,
A part of the regeneration gas from the regeneration gas introduction part is fed to the catalyst layer through any one of the first to third spaces, some spaces, and the fourth space, whereby the catalyst is regenerated. It is characterized by being.

In order to increase the reaction efficiency in the catalytic cracking reaction, it is indispensable to ensure a uniform reaction temperature of the catalyst layer and uniform contact with the feedstock, and the catalyst layer in the regeneration process of the solid catalyst (hereinafter referred to as “catalyst”). It is important to ensure a uniform regeneration temperature (including ensuring the combustion reaction temperature of coke) and a uniform flow of regeneration gas to the catalyst surface and sufficient contact time. In particular, from the inventor's knowledge that coke adhering to the catalyst surface is more likely to be produced as the reaction temperature during the catalytic cracking reaction is higher, it is important to improve the efficiency of regeneration in the vicinity of the heating section. The present invention addresses these issues.
(A) The catalyst is heated not only from the periphery of the catalyst layer but also by providing a heating portion inside the catalyst layer and heating it. (B) Introduction or derivation of feedstock oil or regeneration gas is predetermined. This is performed through a space and a plate through which gas and liquid can circulate, thereby suppressing the drift of raw material oil and regenerated gas, making contact with the catalyst uniform, and ensuring a predetermined contact time by using such a plate as a resistance. (C) In particular, in the vicinity of the heating portion provided inside the catalyst layer, the flow resistance of the regeneration gas is reduced by the space (fourth space) provided via the plate, and the catalyst surface with a large amount of coke is deposited. By preferentially contacting with the regeneration gas, the attached and accumulated coke is efficiently removed, and by suppressing the agglomeration, the packed catalyst is leveled so that high catalyst efficiency can be maintained. And constitute efficient renewable reactor, it is possible to provide a diesel fuel reactor for producing the cracked oil in higher yields can be obtained.

The present invention is the above-described reactor, wherein any one or some of the plates A to C are constituted by a porous partition plate having a dispersion function, and the distribution within the catalyst layer is uniform. It is characterized by increasing.
As described above, it is important to ensure uniform contact between the raw material oil or the regeneration gas and the catalyst in the catalyst layer. In particular, the regeneration gas tends to form a drift due to a small difference in flow resistance, so that the plate portion plays an important role in the configuration of the present invention. Specifically, the plate part is composed of a porous partition plate, and its dispersion function is used to ensure a uniform distribution inside the catalyst layer, to suppress the drift of raw material oil and regenerated gas, Can be made uniform.

The present invention is the reactor described above, wherein the second heating unit is configured by a plate-shaped body having a heating member, and the plate-shaped body is disposed in a vertical direction with respect to the catalyst layer. To do.
The uniformity of temperature in the catalyst layer greatly affects not only the catalytic cracking reaction of the raw material oil but also the combustion reaction of coke during the regeneration of the catalyst. The present invention is a knowledge obtained as a result of studying the shape of the heating unit together with the arrangement of the heating unit inside the catalyst layer, and by increasing the heat transfer area of the heating unit with a plate-shaped body, the catalyst layer A more uniform temperature distribution can be formed. Further, by arranging the plate-shaped body in the longitudinal direction with respect to the catalyst layer, the flow of gas and liquid is regulated, and combined with the dispersed and uniform flow, it is heated uniformly without drift. Smooth distribution can be formed.

The present invention is the above-described reactor, wherein the regeneration gas introduction section includes a plurality of first gas introduction sections provided in any one or several spaces of the first to fourth spaces, and a plurality of the catalyst layers. A second gas introduction part having a nozzle, and one or more of the first to third spaces from the first gas introduction part, and / or the fourth space, and / or the second gas introduction part. From the above, the regeneration of the catalyst is performed by feeding the regeneration gas to the catalyst layer.
As described above, it is important to ensure uniform contact between the regeneration gas and the catalyst in the catalyst layer. In particular, when the particle size of the catalyst is small or the packing amount is large, a minute difference in flow resistance due to the flow of the regeneration gas occurs, and a drift is easily formed. By inserting a plurality of nozzles into the layer and feeding the regeneration gas, the catalyst and the regeneration gas can be contacted more evenly inside the catalyst layer.

The present invention is the reactor described above, wherein the catalyst layer is divided into a plurality of overlapping catalyst layers, and a plate D provided above the upper plate B and the lower catalyst layer between the catalyst layers. It has 1 or 2 or more 5th space formed from these.
The flow of the raw material oil and the regenerated gas inside the catalyst layer forms a drift to a specific flow path with long-term use. The present invention aims to improve catalytic cracking reaction efficiency and regeneration efficiency of each catalyst layer unit by forming a plurality of overlapping catalyst layers. That is, by reducing the flow of the feed oil and the regeneration gas, the drift is reduced, and at the same time, after the feed oil and the regeneration gas that have passed through one catalyst layer are buffered by the space provided between the catalyst layers, By being introduced into the catalyst layer, it is possible to ensure very high uniformity as a whole catalyst layer, and it is possible to ensure high catalytic cracking reaction efficiency and regeneration efficiency with the minimum capacity catalyst layer.

The present invention is the reactor described above, wherein the oxygen concentration in the regeneration gas is 1 to 10%.
The catalyst can be regenerated mainly by efficiently burning and removing the coke deposited and accumulated on its surface. Since the reaction heat generated by this combustion reaction heats the catalyst, there is a possibility that a superheated state is locally formed on the catalyst surface to which a large amount of coke is adhered. The formation of an overheated state causes not only the catalyst characteristics but also the catalyst itself to be damaged when the temperature exceeds the heat resistance temperature of the catalyst, and causes deterioration of the catalyst characteristics even at temperatures within that range. The present invention aims to prevent such overheating by suppressing the oxygen concentration in the regeneration gas that serves as a combustion aid for such a combustion reaction. As a result of demonstration based on air, it was found that the above range is preferable.

The present invention is a diesel fuel production system using any of the above reactors,
A raw material tank for storing raw oil, a first fractionator for separating light oil from the cracked oil obtained in the reactor, and a light oil fraction from the light oil obtained in the first fractionator. A second fractionator to be recovered; a cooler that cools the light oil fraction recovered by the second fractionator to produce product oil; and the feedstock that is supplied from the feed tank to the reactor. Comprising a feed oil supply line that can be used as a heat medium in the order of the cooler, the second fractionator and the first fractionator and then supplied to the reactor;
The raw oil supply line is installed between a raw oil supply pump for supplying the raw oil to the downstream side, the cooler and the second fractionator, and first preheating for heating the raw oil And a second preheater installed between the second fractionator and the first fractionator for heating the feedstock.
The reactor has the basic functions (a) to (c) described above, and the present invention makes use of such excellent functions to produce a higher yield of cracked oil from the raw material oil, which is even higher. A diesel fuel production system can be constructed that yields a high yield of diesel fuel. In addition, the feed oil is used as the heat medium, and the heat is used in the order of the cooler, the second fractionator, and the first fractionator. The amount of heat consumed can be reduced. Further, by preheating the raw material oil, the temperature range in each fractionator is reduced, and stable temperature control is possible from the start of operation to steady operation. In this way, an unprecedented energy efficient diesel fuel production system can be configured.

The present invention is the diesel fuel production system described above, wherein the second fractionator combusts the remaining fraction fraction collected from the light oil fraction from the light oil, and the combustor. A combustion exhaust gas supply line for supplying a part of the combustion exhaust gas discharged by burning the remainder of the fractionation to the reactor as the regeneration gas, and a combustion exhaust gas supply amount by a feeding means installed in the combustion exhaust gas supply line And a gas supply amount control unit for controlling the above.
According to this configuration, a part of the combustion exhaust gas obtained by burning the remaining fraction separated by the second fractionator with the combustor can be effectively used as the regeneration gas for the catalyst. In other words, the surplus hydrocarbon components generated in the diesel fuel production system according to the present invention are combusted and discharged as clean combustion exhaust gas, and the combustion exhaust gas thus obtained is a gas having a lower oxygen concentration than air. It is effectively used as a regeneration gas for the reactor. Combustion exhaust gas is used, and it is not necessary to dilute the air and use it as a regeneration gas.

The whole block diagram which illustrates the basic composition of the reactor concerning the present invention. The block diagram which shows the 2nd structural example of the reactor which concerns on this invention. The block diagram which shows the 3rd structural example of the reactor which concerns on this invention. The block diagram which shows the example of 1 structure of the diesel fuel manufacturing system using the reactor which concerns on this invention. The block diagram which shows the other structural example of the diesel fuel manufacturing system using the reactor which concerns on this invention. The whole block diagram which illustrates the apparatus used in order to obtain diesel fuel oil from the waste cooking oil which concerns on a prior art.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. A reactor according to the present invention (hereinafter referred to as “reactor”) includes a reaction tank having a catalyst layer filled with a catalyst (solid catalyst), and produces cracked oil composed of hydrocarbons from raw material oil by catalytic cracking. . A heating part comprising a first heating part provided around the reaction tank, a second heating part provided in the catalyst layer, and at least a plate A provided in the circulating part of the catalyst layer, and a lower part of the catalyst layer Between the plate B that is provided and the plate C that is provided around the second heating unit, and the first space provided above the catalyst layer, between the plate A and the inner surface of the reaction tank A second space provided between the plate B and the inner surface of the reaction vessel, a fourth space provided between the plate C and the second heating unit, each having a predetermined volume. And a catalyst regeneration treatment unit comprising a regeneration gas introduction part and a gas discharge part provided in the reaction tank, and a part of the regeneration gas from the regeneration gas introduction part is in the first to third spaces. The catalyst layer is supplied through any one or several of the spaces and the fourth space. By being, wherein the catalyst is regenerated.

<First configuration example of reactor>
As one embodiment of the reactor, a schematic overall configuration of a first configuration example is shown in FIGS. 1 (A) and (B). A cross section from the front of the reactor 10 is shown in FIG. 1 (A), and an XX cross section from the top is shown in FIG. 1 (B). The reactor 10 includes a catalyst layer 2 filled with a catalyst for producing cracked oil from raw material oil, an introduction portion for introducing the raw material oil into the reaction tank 1, a delivery portion 4 for feeding gas phase cracked oil, and a liquid A reaction unit having a discharge unit 5 for discharging the phase residue, a regeneration gas introduction unit 6 for introducing the regeneration gas into the reaction tank 1, and a gas discharge unit 7 for discharging the regeneration gas (exhaust gas) used for regeneration of the catalyst. A tank 1 is provided. The reactor 10 is provided with a heating means (first heating part H1) around the reaction tank 1 in order to maintain a reaction temperature for forming a stable decomposition reaction, and a second heating is provided inside the catalyst layer 2. Part H2 is provided. On the upper part of the catalyst layer 2, an injection unit 3 a is provided in which the raw material oil introduced from the introduction unit 3 is injected so as to diffuse widely. Around the catalyst layer 2, plates (plates A to C) through which gas and liquid can flow are arranged to partition the catalyst layer 2 and a space (second to fourth spaces S <b> 2 to S <b> 4) having a predetermined volume. And a uniform flow of the raw material oil and the regeneration gas in the layer. At this time, in addition to the plates A to C, by providing a plate D that forms a partition between the catalyst layer 2 and the first space S1 above the catalyst layer 2, it is possible to further form a uniform flow of the raw material oil. it can.

  The reactor 10 is preferably a metal pressure vessel that can withstand the use conditions (pressure) of the decomposition reaction. Generally, a pressure vessel made of vertical cylindrical carbon steel or stainless steel (SUS) is used. The configuration of the reactor 10, such as the reaction tank 1, the catalyst layer 2, the plates A to C (including the plate D) or the spaces S1 to S4, the capacity and the arrangement of the heating parts H1 and H2, etc. It is determined from the introduction amount and characteristics of the raw material oil (type and use of the oil), reaction conditions and economical conditions (size of the reactor 10).

  The plates A to D are composed of plates that can be circulated. The uneven flow of the raw material oil and the regeneration gas can be suppressed, and the contact with the catalyst can be performed uniformly. For example, when a catalyst having a particle diameter of 3 mm is used, a punching metal having an aperture ratio of 40% having holes of 2 mm is used. At this time, any or some of the plates A to D are formed of a porous partition plate and function as a rectifying layer, whereby the rectified raw material oil or raw material gas is guided to the catalyst layer 2. Further, the uniformity of distribution inside the catalyst layer 2 can be improved. Specifically, by using a porous plate made of a metal such as a sintered metal plate or a ceramic and having a number of pores sufficiently smaller than the catalyst particles, a high dispersion function of the regeneration gas can be obtained. However, it is preferable that the holes be fine enough to uniformly disperse the raw material oil and the raw material gas, and the pressure loss of the plates A to D is not excessive.

[Production function of cracked oil]
The raw material oil is introduced into the reaction tank 1 through the introduction unit 3 and is widely injected over the entire upper part of the catalyst layer 2 by the injection unit 3a. When the plate D is provided while the sprayed raw material oil is diffused in the space S <b> 1, the raw material oil is further dispersed in the plate D through which gas and liquid can flow and transferred to the catalyst layer 2. Combined with the diffusion by the injection unit 3a, the raw material oil can be dispersed throughout the upper layer of the catalyst layer 2, the drift of the raw material oil can be suppressed, and the catalyst layer 2 can be uniformly contacted with the catalyst. The raw material oil transferred to the upper layer of the catalyst layer 2 is converted into cracked oil composed of hydrocarbons by a cracking reaction by contacting with the heated catalyst while passing through the catalyst layer 2. At this time, a part of the catalyst generates a small amount of coke and adheres to the catalyst surface. Most of the converted cracked oil becomes a gas phase component containing light oil and a light oil fraction under high temperature conditions, and again a processing device (not shown) for producing diesel fuel from the supply section 4 via the plate D and the space S1. )). The liquid phase residue of the converted cracked oil is stored in the space S3 via the plate B provided at the lower part of the catalyst layer 2, and is discharged from the discharge unit 5 after storing a predetermined amount or continuously. The gas phase component of the cracked oil can be fed, for example, by a suction means (not shown) provided at the subsequent stage. Alternatively, a carrier gas for conveyance (for example, it is preferable to use an inert gas such as nitrogen gas, water vapor, or off gas) can be introduced and fed. This carrier gas may be supplied continuously during operation, or may be supplied according to the operation status.

  The raw material oil to be introduced is, for example, waste edible oil, vegetable oil, animal oil, or various mineral oils alone or in combination. Examples of the waste cooking oil include tempura oil and fried oil. Examples of vegetable oils include rapeseed oil, soybean oil, sesame oil, safflower oil, cottonseed oil, rice oil, peanut oil, sunflower oil, corn oil, olive oil, palm oil, coconut oil, jatropha oil, peanut oil and the like. Examples of animal fats include beef tallow (hett), pork oil (lard) and the like. Examples of the mineral oil include various hydrocarbon-based mineral oils. In order to prevent poisoning of the catalyst and blockage of the flow path, the raw material oil is preferably introduced into the reaction tank 1 in a state in which pretreatment such as dust removal or dehydration has been performed in advance.

The catalyst used in the catalytic cracking method is preferably an inorganic solid catalyst. In particular, when an alkali metal or alkaline earth metal compound is used as a catalyst, a light oil-like decomposition oil and carbon dioxide, propane and other light oils are decomposed by a decarboxylation decomposition reaction that cleaves the ester bond portion of the oil. It can be decomposed into gas and does not require chemicals such as alcohol and caustic potash as in the conventional transesterification method, and does not generate waste such as glycerin and wastewater, and produces biodiesel fuel equivalent to commercial light oil It has features such as As cracked oil, for example, a hydrocarbon mixture mainly composed of olefin / paraffin having 9 to 20 carbon atoms can be obtained. Specific examples of the catalyst include zeolite, ion exchange resin, lime, clay, metal oxide, metal carbonate, composite oxide such as SiO ₂ —MgO and SiO ₂ —CaO, and supported metal oxide. In particular, a supported metal oxide of SiO ₂ —MgO is preferable. When this supported metal oxide of SiO ₂ —MgO is used, the yield of the obtained diesel fuel (light oil) is preferably 60% or more. The shape of the catalyst is not particularly limited as long as the flow resistance is small and the surface area can be sufficiently secured. For example, a granular material or a pellet-shaped material having a particle diameter of 2 to 5 mm is used. In the reactor 10, the method of fixing the catalyst by the plate portion has been exemplified, but the present invention is not particularly limited to this, and various modes such as configuring the fixed catalyst reactor 10 by fixing the catalyst to the fixing member are possible. Needless to say.

  For example, when an alkali metal or alkaline earth metal catalyst is used, the reaction temperature of the catalytic cracking method in the reactor 10 is preferably set to about 400 to 500 ° C, more preferably about 400 to 450 ° C. preferable. When the temperature is lower than 400 ° C., the reaction efficiency may be lowered. When the temperature is higher than 500 ° C., local heat may be generated on the catalyst surface due to the heat of reaction accompanying the decomposition reaction, and the catalyst may be deteriorated. The temperature of the catalyst layer 2 is maintained by controlling the heating by the first heating unit H1 provided around the reaction tank 1 and the second heating unit H2 provided inside the catalyst layer 2, and the uniformity thereof is maintained. Can be planned. At this time, since the fourth space is provided via the plate C in the vicinity of the second heating unit H2, the generation of coke on the catalyst surface in the vicinity of the second heating unit H2 can be suppressed. Moreover, the structure in particular of heating part H1, H2 is not restrict | limited, For example, the heat exchanger etc. which used an electric heater, a burner, or hot air, steam, waste gas waste heat, etc. are mentioned.

  Here, as shown in FIGS. 1A and 1B, the second heating unit H <b> 2 is configured by a plate-shaped body having a heating member, and the plate-shaped body is disposed in the vertical direction with respect to the catalyst layer 2. It is preferred that A more uniform temperature distribution can be formed in the catalyst layer by widening the heat transfer area of the heating section with the plate-shaped body. Further, by arranging the plate-shaped body in the longitudinal direction with respect to the catalyst layer, the flow of gas and liquid is regulated, and combined with the dispersed and uniform flow, it is heated uniformly without drift. Smooth distribution can be formed.

[Catalyst regeneration function]
Coke, which is a by-product of the cracking reaction, adheres to the catalyst surface used for the cracking reaction of the feedstock oil. The deposition of coke on the surface of the catalyst causes a decrease in the catalyst function, and the regeneration function of the catalyst is impaired as coke agglomerates, making it impossible to regenerate. Therefore, it is necessary to perform a regeneration process after a predetermined period of use. In the reactor 10, it was found that regeneration can be performed by introducing a regeneration gas containing a predetermined amount of oxygen into the catalyst layer 2 and mainly oxidizing and burning the coke to remove it.

  Here, the regeneration gas preferably has an oxygen concentration of 1 to 10%, more preferably 5 to 10%. Since the reaction heat generated by the combustion reaction on the catalyst surface heats the catalyst, there is a possibility that a superheated state is locally formed on the catalyst surface to which a large amount of coke is adhered. The formation of an overheated state causes not only the catalyst characteristics but also the catalyst itself to be damaged when the temperature exceeds the heat resistance temperature of the catalyst, and causes deterioration of the catalyst characteristics even at temperatures within that range. Such a superheated state can be generated by suppressing the oxygen concentration in the regeneration gas that serves as a combustion reaction auxiliary agent. As a result of verification based on air, the combustion reaction was not sufficiently performed at less than 1%, and the catalyst characteristics were deteriorated due to the residual coke. When the ratio exceeded 10%, local combustion in the catalyst layer 2 was observed. Overheating was observed. As a specific regeneration gas, for example, a mixed gas of air and nitrogen gas, combustion exhaust gas, or the like can be used. At this time, it is preferable to measure the oxygen concentration in the regeneration gas.

The regeneration gas introduced into the reaction tank 1 from the regeneration gas introduction unit 6 is fed to the catalyst layer 2 through the second to fourth spaces S2 to S4 and the plates A to C. When the regeneration gas contacts the heated catalyst while passing through the catalyst layer 2, the coke on the catalyst surface is converted into carbon dioxide (CO ₂ ) or water (H ₂ O) by an oxidation reaction (combustion reaction). The catalyst activity can be recovered. A regeneration gas (exhaust gas) that passes through the catalyst 2 and contains CO ₂ and H ₂ O is discharged from the gas discharge portion 7 via the plate D and the first space S1. Note that the regeneration gas introduction unit 6 can be configured not only in the configuration provided in the third space S3 but also in any of the first, second, fourth spaces S1, S2, S4, or in a plurality of spaces. .

  Any or some of the plates A to D are formed of a porous partition plate having a gas dispersion function as described above. By utilizing the gas dispersion function, a uniform gas flow inside the catalyst layer 2 can be ensured. Further, since the porous partition plate functions as a flow resistance against the gas flow, the pressure inside the catalyst layer 2 is increased (increase the residence time) together with the flow resistance inside the catalyst layer 2 to increase the regeneration gas and the catalyst. This ensures a predetermined contact time and contributes to an improvement in reaction efficiency.

  In the reaction tank 1, the raw material gas from the third space S3 rectified by the plate B is led to the catalyst layer 2 from the entire lower surface, and rises in the layer while contacting the catalyst in a heated state. It is heated by a combustion reaction (exothermic reaction) with coke on the catalyst surface and contributes to the heating of the upper layer of the catalyst layer 2. The raw material gas from the second space S2 rectified by the plate A is led to the catalyst layer 2 from the side surface, merges with the raw material gas from the third space S3, and rises in the layer while contacting the catalyst in a heated state. . This has a function of rapidly transmitting the heat from the first heating unit H1 to the catalyst layer 2 and contributes to stabilization of the temperature of the catalyst layer 2. The raw material gas from the fourth space S4 rectified by the plate C is led from the center to the catalyst layer 2 and merges with the raw material gas from the third space S3 and rises in the layer while contacting the catalyst in a heated state. To do. This has a function of quickly transmitting the heat from the second heating part H2 to the catalyst layer 2 and contributes to stabilization of the temperature of the catalyst layer 2. In particular, by providing the plate-shaped second heating part H2 in the longitudinal direction with respect to the catalyst layer 2, the function is further enhanced.

[Second Example of Reactor Configuration]
As another configuration example of the reactor 10, the regenerative gas is not only from the regenerative gas introduction unit 6 (first gas introduction unit), but also the second gas introduction unit 8 having a plurality of nozzles 8 a inserted into the catalyst layer 2. FIG. 2 shows a configuration (second configuration example) that is also introduced from FIG. It is preferable to regenerate the catalyst in the catalyst layer 2 evenly by feeding the regeneration gas from a plurality of locations in the catalyst layer 2. It is possible to prevent uneven flow of the regeneration gas due to variations in coke adhering to the catalyst surface, and in particular, when the catalyst particle size is small or the packing amount is large, there is a small difference in flow resistance due to regeneration gas flow. Therefore, it is possible to more evenly contact the catalyst and the regeneration gas inside the catalyst layer by feeding regeneration gas from a plurality of locations in the catalyst layer 2. .

[Third configuration example of the reactor]
A third configuration example of the reactor 10 is shown in FIG. The catalyst layer 2 is divided into a plurality of overlapping catalyst layers 2a and 2b, and is formed between the catalyst layers 2a and 2b from a plate Ba below the upper catalyst layer 2a and a plate Db above the lower catalyst layer 2b. A fifth space S5. Inside the catalyst layer 2 composed of a catalyst having a small particle size or a large amount of catalyst, the flow of the raw material oil and the regeneration gas tends to form a drift to a specific flow path, and adheres to the catalyst surface with long-term use. Diffusion is likely to occur due to the difference in the amount of coke. By forming the catalyst layers 2a and 2b divided into a plurality of overlapping layers, the catalytic cracking reaction efficiency and the regeneration efficiency of each catalyst layer 2a and 2b can be improved, and the capacity of the entire catalyst layer can be reduced. In addition, the raw material oil or the regenerated gas that has passed through the catalyst layer 2a or 2b is once buffered by the space S5 and then introduced into the next catalyst layer 2b or 2a, so that the entire catalyst layer has very high uniformity. It is possible to ensure high catalytic cracking reaction efficiency and regeneration efficiency with a minimum capacity.

Moreover, about each catalyst layer 2a, 2b, without having the structure and function of each site | part similar to a 1st structural example, each catalyst layer 2a, 2b can be made into a different structure as follows.
(I) The capacity of the catalyst layer 2b can be made smaller than the capacity of the catalyst layer 2a, and the raw material oil that has not been treated in the catalyst layer 2a can be decomposed in the catalyst layer 2b. At this time, by making the temperature of the catalyst layer 2b higher than that of the catalyst layer 2a (for example, about 50 ° C.), untreated raw material oil can be further reduced, and the high-temperature decomposition component in the raw material oil is decomposed. be able to.
(Ii) By changing the type and shape of the catalyst of the catalyst layers 2a and 2b, the reaction tank 1 corresponding to the specifications of the raw material oil can be configured. That is, the catalyst layer 2a is composed of a highly efficient type and shape of the catalyst with respect to a predetermined main component in the raw material oil, and the catalyst layer 2b is composed of a highly efficient type and shape of the catalyst with respect to other components. As a result, the entire raw oil can be decomposed.

<Diesel fuel production system using reactor>
Next, a diesel fuel production system (hereinafter referred to as “the present system”) using the reactor will be described in detail. The system includes a raw material tank, a reactor, a first fractionator, a second fractionator, a cooler, and a raw material oil supplied to the reactor from the raw material tank, the cooler, the second fractionator, and the first A raw material oil supply line that can be used as a heat medium in the order of the fractionator and then supplied to the reactor is provided. The raw material oil supply line includes a raw material oil supply pump, a first preheater, and a second preheater. It is characterized by that. This system makes it possible to produce a higher yield of cracked oil from the feedstock and to obtain a higher yield of diesel fuel by making use of the reactor having the excellent functions of the reactor.

  Hereinafter, the details of the system will be described based on the configuration example shown in FIG. This system was obtained in a reactor 10 having a raw material tank 20 for storing raw material oil, a catalyst 10 for converting the raw material oil supplied from the raw material tank 20 into cracked oil made of hydrocarbons, and the reactor 10. A first fractionator 31 for separating light oil from cracked oil, a second fractionator 32 for recovering a light oil fraction from the light oil obtained in the first fractionator 31, and a second fractionator 32. A cooler 40 that cools the recovered light oil fraction to produce product oil, and a product oil tank 50 that stores product oil (diesel fuel) cooled by the cooler 40 to become liquid. The raw material oil supplied from the raw material tank 20 to the reactor 10 can be supplied to the reactor 10 after being used as a heating medium in the order of the cooler 40, the second fractionator 32, and the first fractionator 31. The raw material oil supply line L is provided. In this raw material oil supply line L, the front stage supply line L1 passes through the raw material oil supply pump 60 and the cooler 40 for supplying the raw material oil downstream, and the middle stage supply line L2 includes the cooler 40 and the second supply line L2. Passing through the first preheater 71 and the second fractionator 32 installed between the fractionator 32 and heating the feedstock, the latter supply line L3 is connected to the second fractionator 32 and the first fractionator. It passes through the second preheater 72 and the first fractionator 31 that are installed between the vessel 31 and heats the feedstock. Regeneration of the reactor 10 can be performed in the same manner as in the first to third configuration examples.

  Specifically, the raw material oil in the raw material tank 20 is at normal temperature (ambient environmental temperature), and is sent as a heat medium of the cooler 40 at normal temperature, where the light oil fraction obtained by the second fractionator 32 The heat is exchanged with (for example, 150 to 200 ° C.) and sent to the first preheater 71. The temperature of the raw material oil which passes the cooler 40 and is sent to the 1st preheater 71 is 50-80 degreeC, for example. Next, the raw material oil is heated (or not heated) by the first preheater 71 and is sent as a heat medium for the second fractionator 32, where the gas component (lighter) in the second fractionator 32 is sent. Oil gas) is exchanged with heat and sent to the second preheater 72. The temperature of the raw material oil which passes the 2nd fractionator 32 and is sent to the 2nd preheater 72 is 150-240 degreeC, for example. Next, the raw material oil is heated (or not heated) by the second preheater 72 and sent as a heat medium of the first fractionator 31, where the gas component (gas) in the first fractionator 31 is sent. Phase cracked oil) and heat-exchanged to reactor 10. The temperature of the feedstock that passes through the first fractionator 31 and is sent to the reactor 10 is, for example, 300 to 350 ° C. Next, the temperature in the reactor 10 is set to, for example, 400 to 450 ° C., the raw material oil is brought into contact with the catalyst in the catalyst layer 2 to perform the decomposition reaction, and the obtained gas-phase decomposed oil is decomposed oil gas line La To the first fractionator 31. The temperature of the cracked oil in the gas phase sent to the first fractionator 31 is, for example, 380 to 420 ° C. Next, the gas phase cracked oil is fractionated in the first fractionator 31 to obtain a light oil gas, and this light oil gas is sent to the second fractionator 32 through the light oil gas line Lb. The temperature of the light oil gas sent to the 2nd fractionator 32 is 250-300 degreeC, for example. In the second fractionator 32, the light oil gas is separated into a light oil fraction and a fractional fraction (for example, combustible gas, naphtha, kerosene, etc.), and this fractional fraction is passed through a fractional distillation line Le. The light oil fraction (light oil distillate gas) discharged from the second fractionator 32 is sent to the cooler 40 through the light oil distillate gas line Lc. The temperature of the gas oil distillate gas sent to the cooler 40 is, for example, 150 to 200 ° C. Next, the light oil distillate gas is cooled in the cooler 40 to obtain liquid product oil (diesel fuel), which is sent to the product oil tank 50 through the product oil line Ld and collected. By setting the optimal processing and reaction conditions for obtaining diesel fuel from such feedstock, high yields of gas phase cracked oil, light oil gas, gas oil distillate gas are produced, and even higher yields are obtained. Diesel fuel (product oil) can be obtained.

  Here, in the reactor 10, the raw material oil that passed through the first fractionator 31 was widely injected over the entire upper part of the catalyst layer 2 through the introduction part 3, and heated while passing through the catalyst layer 2. By contacting the catalyst, it is converted into cracked oil composed of hydrocarbons by a cracking reaction. The obtained gas phase cracked oil is fed through the feed unit 4 and sent to the first fractionator 31 through the cracked oil gas line La. In addition, the regeneration of the reactor 10 is performed by stopping the supply of the raw material oil to the reactor 10, introducing the regeneration gas from the regeneration gas introduction unit 6, and regenerating the catalyst. The regeneration gas introduced from the regeneration gas introduction unit 6 is fed to the catalyst layer 2. When the regeneration gas contacts the heated catalyst while passing through the catalyst layer 2, the catalytic activity can be recovered. The exhaust gas that has passed through the catalyst 2 is discharged from the gas discharge unit 7.

  In addition, instead of one reactor 10, two reactors 10 and 10 are arranged in parallel, and catalytic cracking reaction is performed in one reactor 10 to generate cracked oil, and catalyst is produced in the other reactor 10. It is possible to perform the reproduction process.

[Other configuration examples of this system]
Next, in the present system, a configuration example in which a part of the combustion exhaust gas obtained by burning the remaining fraction separated by the second fractionator 32 in the combustor 80 is used as a regeneration gas for the catalyst. As shown in FIG. Combustor 80 for combusting the remaining fraction fraction recovered from the light oil in the second fractionator 32, and the combustion exhaust gas discharged by burning the fraction residue in the combustor 80. A flue gas supply line Lr for supplying a part of the flue gas to the reactor 10 as a regeneration gas, and a gas supply amount control unit for controlling the flue gas supply amount by a fan 61 (corresponding to the feeding means) installed in the flue gas supply line Lr ( (Not shown).

  In this system, the fraction remaining fraction includes, for example, combustible gas, naphtha, kerosene and the like. The flue gas obtained by burning this in the combustor 80 has a lower concentration than air, but contains a predetermined amount of oxygen (about 1 to 10%). Therefore, a part of it can be used as a regeneration gas for the reactor 10. By using the combustion exhaust gas for regeneration of the catalyst, it is possible to suppress local excessive combustion exceeding the heat-resistant temperature of the catalyst and to effectively regenerate the entire catalyst. Excess hydrocarbon components generated in this system are combusted and discharged as clean flue gas, and by using a part of them effectively, there is no need to newly dilute the air to produce regenerated gas, Resources and energy can be used effectively. Moreover, since combustion exhaust gas components other than oxygen act as a cooling medium, the supply amount of the regeneration gas can be increased, and as a result, the catalyst of the reactor 10 can be rapidly regenerated. Furthermore, by increasing the amount of regenerated gas, the flow velocity passing through the catalyst layer 2 in the reactor 10 increases, gas diffusion into the catalyst layer 2 is promoted, and the entire catalyst can be regenerated uniformly.

  Here, a burner or the like can be used for the combustor 80, for example. The remaining fraction is burned by the combustor 80, and the combustion exhaust gas is discharged through the combustion exhaust gas line Lf. Part of the combustion exhaust gas is fed to the reactor 10 as regeneration gas by a fan 61 provided in the combustion exhaust gas supply line Lr branched from the combustion exhaust gas line Lf. The supply amount of the regeneration gas is controlled by adjusting the rotational speed (flow velocity) of the fan 61 (corresponding to a gas supply amount control unit). The exhaust gas generated by the regeneration of the reactor 10 is fed to the combustor 80 through the exhaust gas line Ls, and is preferably burned here.

  In addition, it is desirable that combustion exhaust gas is combustion-controlled in the combustor 80 so that the oxygen concentration is in the range of 1 to 10%, preferably 5 to 10%. In such a case, for example, an oxygen concentration sensor 90 is attached to the combustion exhaust gas line Lf, and the control unit of the combustor 80 controls the combustion state in accordance with a signal from the oxygen concentration sensor 90. The temperature of the combustion exhaust gas is supplied to the reactor 10 in the range of 200 to 500 ° C., preferably 200 to 300 ° C. so that the combustion of the coke adhering to the catalyst can be maintained and the catalyst does not overheat. It is desirable to do.

[Example 1]
In the configuration of the reactor, the plate portion has a great influence on the catalyst layer, particularly the catalyst layer near the second heating portion. Here, the remaining amount of coke on the catalyst surface in the catalyst layer 2 in the vicinity of the second heating unit H2 was verified by the presence or absence of the plate C in the first configuration example, and the technical effect was verified.

(1) Experimental conditions About the reactor which concerns on a 1st structural example, about 100 hours raw material oil reaction processing is performed on each condition of the presence or absence of the partition plate (plate C) vicinity of the 2nd heating part H2, and after a regeneration process, Comparison of the remaining amount of coke on the catalyst surface around the second heating part H2 was performed. The measurement of coke was performed using a CHN meter (Yanako Analytical Industry, CHN coder: MT-6).

(2) Demonstration results Table 1 shows the amount of coke remaining on the catalyst surface under each condition. When there was no partition plate, the amount of coke was very large. On the other hand, when the partition plate was installed, the amount of coke was greatly reduced. As for the actual state of the catalyst surface, a large amount of coke was agglomerated in the former, and the latter remained in the shape of the catalyst (spherical).

DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Catalyst layer 3 Introduction part 3a Injection part 4 Delivery part 5 Discharge part 6 Regeneration gas introduction part 7 Gas discharge part 10 Reactor AD Plate H1, H2 1st, 2 heating part S1-S4 1st-4th space

Claims (8)

In a reactor comprising a reaction tank having a catalyst layer filled with a solid catalyst, and producing cracked oil composed of hydrocarbons from raw material oil by catalytic cracking,
A heating unit comprising a first heating unit provided around the reaction vessel, a second heating unit provided in the catalyst layer, and
A plate through which gas and liquid can circulate, comprising at least a plate A provided in a circulating portion of the catalyst layer, a plate B provided in a lower portion of the catalyst layer, and a plate C provided around the second heating unit. And
A first space provided above the catalyst layer, a second space provided between the plate A and the inner surface of the reaction vessel, and a second space provided between the plate B and the inner surface of the reaction vessel. Three spaces, a fourth space provided between the plate C and the second heating unit, each of which has a predetermined volume,
A catalyst regeneration treatment section comprising a regeneration gas introduction section and a gas discharge section provided in the reaction tank;
With
A part of the regeneration gas from the regeneration gas introduction part is fed to the catalyst layer through any one of the first to third spaces, some spaces, and the fourth space, whereby the catalyst is regenerated. A reactor for producing diesel fuel.   2. The diesel according to claim 1, wherein any one or some of the plates A to C are formed of a porous partition plate having a dispersion function, and improve the uniformity of circulation in the catalyst layer. Reactor for fuel production.   3. The diesel fuel production according to claim 1, wherein the second heating unit is configured by a plate-shaped body having a heating member, and the plate-shaped body is disposed in a longitudinal direction with respect to the catalyst layer. Reactor. The regeneration gas introduction part is configured by a first gas introduction part provided in any one or some of the spaces 1 to 4 and a second gas introduction part having a plurality of nozzles inserted in the catalyst layer. ,
The regeneration gas is fed to the catalyst layer from the first gas introduction part via any one of the first to third spaces, some spaces and the fourth space, and / or from the second gas introduction part. The reactor for producing diesel fuel according to any one of claims 1 to 3, wherein the catalyst is regenerated.   The catalyst layer is divided into a plurality of overlapping catalyst layers, and one or more first or more second catalyst layers formed from an upper plate B and a plate D provided above the lower catalyst layer between the catalyst layers. The reactor for producing diesel fuel according to any one of claims 1 to 4, wherein the reactor has 5 spaces.   The reactor for producing diesel fuel according to any one of claims 1 to 5, wherein an oxygen concentration in the regeneration gas is 1 to 10%. A diesel fuel production system using the diesel fuel production reactor according to any one of claims 1 to 6,
A raw material tank for storing raw material oil;
A first fractionator for separating light oil from the cracked oil obtained in the reactor;
A second fractionator for recovering a light oil fraction from the light oil obtained in the first fractionator;
A cooler that cools the light oil fraction recovered in the second fractionator into product oil;
The raw material oil that can be supplied to the reactor after using the raw material oil supplied from the raw material tank to the reactor as a heating medium in the order of the cooler, the second fractionator, and the first fractionator. With oil supply line,
The feedstock supply line is
A feed oil supply pump for supplying the feed oil downstream;
A first preheater installed between the cooler and the second fractionator to heat the feedstock;
A diesel fuel production system comprising: a second preheater installed between the second fractionator and the first fractionator to heat the feedstock.   A combustor for combusting the remaining fraction fraction collected from the light oil fraction in the second fractionator, and combustion discharged by burning the fraction fraction fraction in the combustor A combustion exhaust gas supply line that supplies a part of the exhaust gas to the reactor as the regeneration gas; and a gas supply amount control unit that controls a combustion exhaust gas supply amount by a feeding unit installed in the combustion exhaust gas supply line. The diesel fuel production system according to claim 7, wherein:

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